KR101575913B1 - Self-dispersed pigments and methods for making and using the same - Google Patents

Self-dispersed pigments and methods for making and using the same Download PDF

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KR101575913B1
KR101575913B1 KR1020107006246A KR20107006246A KR101575913B1 KR 101575913 B1 KR101575913 B1 KR 101575913B1 KR 1020107006246 A KR1020107006246 A KR 1020107006246A KR 20107006246 A KR20107006246 A KR 20107006246A KR 101575913 B1 KR101575913 B1 KR 101575913B1
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pigment
surface
amp
group
zm
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KR20100074152A (en
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빈센트 싱
마이클 보고몰니
푸탈라스 케이. 수지스
존 피. 케인
다니엘 에이. 울레트
마크 울리히
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센션트 컬러스 인크.
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00Pigment pastes, e.g. for mixing in paints
    • C09D17/003Pigment pastes, e.g. for mixing in paints containing an organic pigment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B68/00Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
    • C09B68/20Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the process features
    • C09B68/24Azo-coupling
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B68/00Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
    • C09B68/40Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
    • C09B68/44Non-ionic groups, e.g. halogen, OH or SH
    • C09B68/443Carboxylic acid derivatives, e.g. carboxylic acid amides, carboxylic acid esters or CN groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B68/00Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
    • C09B68/40Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
    • C09B68/44Non-ionic groups, e.g. halogen, OH or SH
    • C09B68/446Amines or polyamines, e.g. aminopropyl, 1,3,4,-triamino-pentyl or polyethylene imine
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B68/00Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
    • C09B68/40Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
    • C09B68/46Aromatic cyclic groups
    • C09B68/467Heteroaromatic groups
    • C09B68/46776-Membered rings
    • C09B68/46775Triazine
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/48Carbon black
    • C09C1/56Treatment of carbon black ; Purification
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08Treatment with low-molecular-weight non-polymer organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10Treatment with macromolecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/32Inkjet printing inks characterised by colouring agents
    • C09D11/322Pigment inks
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/50Solid solutions
    • C01P2002/52Solid solutions containing elements as dopants
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/22Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/60Optical properties, e.g. expressed in CIELAB-values

Abstract

Reacting a reactive compound having an X- [Y] n reactive group with a second compound NS-ZM to form a substituted reactive intermediate [Y] a -X- (NS-ZM) b . The pigment reacts with the substituted reactive intermediate [Y] a -X- (NS-ZM) b to attach the substituted reactive intermediate to the surface of the pigment to form a surface modified pigment. X may be a sulfonyl, phospholyl, or 1,3,5-triazinyl group, Y may be a halogen leaving group, N may be a basic nucleophilic group, S may be an organic group, and ZM is an ionizing end group . N is an integer of 1 to 3, b is an integer of 1 to 3, and a = nb. When n is equal to or greater than b and b is 2 or 3, each NS-ZM may be the same or different.

Description

[0001] SELF-DISPERSED PIGMENTS AND METHODS FOR MAKING AND USING THE SAME [0002]

Inter-reference to related application - reference

This application claims priority to U.S. Provisional Patent Application No. 60 / 957,596, filed on August 23, 2007 under 35 USC § 119 (e). The entire contents of which are hereby incorporated by reference in their entirety.

Field of use

The present invention relates to a process for the preparation of self-dispersible pigments. More specifically, the present invention relates to surface modification of pigments. Pigments whose surface has been modified via covalent bonding are known in the industry as self-dispersible pigments. Surface modification can be performed in an aqueous environment and can be environmentally friendly. In addition, the present invention relates to end-use applications involving surface-modified pigments, including but not limited to coatings, paints, paper, adhesives, latex, toners, fabrics, will be. Specific examples of end uses include, but are not limited to, printing inks for paper, textiles, fibers, metal decors and plastics, wood stains, writing instruments, and color filters. The present invention also relates to inks such as inkjet inks.

Pigments offer several advantages over water-soluble dyes for inks, coatings, paints, paper, adhesives, latex, toners, fabrics, fibers, wood stains, color filters, and plastics. The pigment can exhibit at least one of greater lightfastness, waterfastness, optical density and edge acuity than the water-soluble dye. Unfortunately, pigments are also more prone to sediment during storage, so their use in the required applications, such as inkjet inks, is initially limited. The advent of media mills, which, in combination with chemical additives for colloidal stability, pulverize pigment particles to sub-micron levels has propelled the use of pigment dispersions in ink jet ink formulations. However, chemical additives can increase the viscosity of the dispersion, making it difficult for ink to be ejected from small orifices of the inkjet printhead. In addition, chemical additives can add significant cost to the manufacture of the materials listed above, and are therefore not economically feasible. Chemical additives, or dispersants may not bond to the surface of the pigment, so stabilization may be insufficient. There remains a need for improved ink compositions for use in ink jet printers, particularly those that solve at least some of the problems typically associated with current dye-based systems and pigment systems using chemical additives. In addition, there remains a need for improved materials using pigments that solve at least some of the problems typically associated with current dye-based systems and pigment systems that use chemical additives.

summary

In one aspect, the present invention can provide a pigment modification method that can include reacting cyanuric chloride with about 3 equivalents of a secondary compound or a mixture of secondary compounds to displace all reactive chlorine to form the substituted triazine have. Substituted triazines can react with the surface of the pigment to form a surface modified pigment.

In another aspect, the present invention provides a process for preparing a substituted reactive intermediate [Y] a -X- (NS-ZM) b by reacting a reactive compound having an X- [Y] n reactive group with a secondary compound NS- To provide a pigment modification method which can be incorporated. The method may also include forming a surface modified pigment by reacting the pigment with the substituted reactive intermediate [Y] a -X- (NS-ZM) b to attach the substituted reactive intermediate to the surface of the pigment . X may be a sulfonyl, phosphoryl, or 1,3,5-triazinyl group. Y may be a halogen leaving group, N may be a nucleophilic group, S may be an organic group, and ZM may be an ionizing end group. N may be an integer of 1 to 3, b may be an integer of 1 to 3, and a = nb. When n is equal to or greater than b and b is 2 or 3, each NS-ZM may be the same or different.

In another aspect, the present invention can provide a pigment modification method, which may include attaching a reactive group to the surface of the pigment. The reactive group can then be replaced with an organic substrate having an ionizing end group. The pigments include red pigment 122, violet pigment 19, violet pigment 23, red pigment 202, red pigment 188, yellow pigment 155, yellow pigment 97, green pigment 7, blue pigment 15: 3, blue pigment 15: ≪ / RTI >

In a further aspect, the present invention may provide a pigment modification method which may include attaching the reactive group X-Y to the surface of the pigment. Subsequently, Y can be replaced with an organic substrate N-S-ZM to form a surface-modified pigment with X-N-S-ZM attached thereto. X may be a sulfonyl, phosphoryl, or 1,3,5-triazine group. Y may be fluorine, chlorine, bromine, or iodine. N may be an amine, an imine, a pyridine, or a thiol group. S may be a substituted or unsubstituted alkyl, aryl, or polymer chain having a molecular weight in the range of from about 300 to about 8000. Z may be a carboxyl, sulfonyl, phenolic, phospholyl, ammonium, trimethylammonium, or tributylammonium group. M can be a halide, a negatively charged ion, a salt in the form of a proton, or a salt in the form of a cation.

Other aspects of the invention will be apparent upon consideration of the detailed description and the accompanying drawings.

1 shows a low resolution X-ray photoelectron spectroscopy (XPS) spectrum of untreated carbon black samples and carbon black samples from Examples 1, 20, 31,
Figure 2 shows the high resolution N1s XPS spectra for untreated carbon black samples and carbon black samples from Examples 1, 20, 31 and 41.
Figure 3 shows a high resolution O1s XPS spectrum for untreated carbon black samples and carbon black samples from Examples 1, 20, 31, and 41.
Figure 4 shows a high resolution S2p XPS spectrum for untreated carbon black samples and carbon black samples from Examples 1, 20, 31 and 41.
Figure 5 shows the low-resolution XPS spectra for the untreated blue pigment 15 sample and the blue pigment 15 sample from Examples 7, 9, 11, 16, and 42.
Figure 6 shows a high resolution O1s XPS spectrum for a sample of untreated blue pigment 15 and 15 samples of blue pigment from Examples 7, 9, 11, 16 and 42.
Figure 7 shows the high resolution Na1s XPS spectra for the untreated blue pigment 15 samples and the blue pigment 15 samples from Examples 7, 9, 11, 16,
Figure 8 shows a low-resolution XPS spectrum for the red pigment 122 sample from the untreated red pigment and the red pigment 122 sample from Examples 14, 21, 37, and 45.
Figure 9 shows the high resolution O1s XPS spectrum for the red pigment sample No. 122 from the untreated red pigment sample and the red pigment sample from Examples 14, 21, 37, and 45. FIG.
10 shows high resolution Na1s XPS spectra for red pigment 122 samples from Examples 14, 21, 37, and 45. FIG.
11 shows a high resolution S2p XPS spectrum for red pigment 122 samples from Examples 14, 21, 37, and 45. FIG.
Figure 12 shows a low-resolution XPS spectrum for the yellow pigment 74 sample from the untreated yellow pigment 74 and the yellow pigment 74 sample from Examples 15, 29, and 46.
Figure 13 shows a high resolution C1s XPS spectrum for the yellow pigment 74 sample from the untreated yellow pigment 74 and the yellow pigment 74 sample from Examples 15, 29 and 46.
Figure 14 shows the high resolution O1s XPS spectrum for the yellow pigment 74 sample from the untreated yellow pigment 74 and the yellow pigment 74 sample from Examples 15, 29 and 46.

Before describing in detail certain embodiments of the invention, it is to be understood that the invention is not limited to applying the invention to the details of construction and arrangement of components set forth in the following description. The invention is capable of other embodiments and of being practiced or carried out in various ways. It is also to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting. As used herein, the terms "comprising", "comprising", or "having" and variations thereof mean inclusion of the items listed thereon and equivalents thereof as well as additional items.

It is also understood that any numerical range mentioned herein includes all values from a low value to a high value. For example, where a concentration range is described as 1% to 50%, values such as 2% to 40%, 10% to 30%, or 1% to 3% are intended to be expressly recited herein. It is to be understood that this is merely an example of what is specifically intended, and the combination of all possible values in between, including the recited lowest and highest values, shall be regarded as being expressly set forth herein.

In one embodiment, the present invention provides a pigment modification method. The method may include attaching the organic group to the charged terminal group (negative or positive) through intermediation of the reactive molecule to produce a surface stabilized modified pigment. Without being limited by theory, it is believed that stabilization is achieved by an equivalent distribution of similarly charged groups covalently attached to pigment particles of sub-micron size by repulsion.

In another embodiment, the present invention provides a pigment modification method. The method may comprise a chlorosulfonation step to form a reactive sulfonyl chloride intermediate which is then reacted with a suitable organic molecule as described above. In one aspect, the degree of chlorosulfonation may be increased to obtain a liquid gel or micelle-like composition, which forms a stable dispersion upon milling with the untreated pigment.

In another embodiment, the invention provides a dispersion comprising a self-dispersible pigment formed by the reaction of a pigment with a reactive intermediate attached to a suitable organic molecule as described above. The selection of stable reactive intermediates in an aqueous environment is another aspect of the present invention.

In another embodiment, the present invention provides a pigment modification method which can include attaching a reactive group to the surface of the pigment, and then replacing the reactive group with an organic substrate having an ionizing end group.

In a further embodiment, the present invention provides a dispersion comprising from about 0.01 to about 1.0 mMole of S per g of pigment and from about 0.01 to about 2.0 mMole of active hydrogen, and a water-containing self-dispersible pigment. In another embodiment, the present invention provides a dispersion comprising from about 0.06 to about 0.7 mMole of S and from about 0.07 to about 1.6 mMole of active hydrogen per gram of pigment, and a water-containing self-dispersible pigment.

Manufacturing method of self-dispersible pigment

One aspect of the invention relates to a process for the preparation of stable self-dispersible pigments.

As used herein, the term "pigment" means insoluble in a solvent medium, which is used to impart color to a substrate, such as plain paper or coated paper, film and other types of receiving media. The pigment may be black as well as other colors.

The term "self-dispersible" pigment as used herein refers to a pigment having a stable group covalently attached to its surface, such that the pigment forms a stable aqueous dispersion without any additional dispersants.

As used herein, the term "stable" means that, when the dispersion is stored over a period of at least about 3 months to 6 months to 2 years at ambient temperature, the dispersion has a major property , At least one of surface tension, and pH), as measured by a change in the thickness of the substrate. Accelerated testing methods include thermal stability testing at about 70 ° C for about one week or more, or thermal stability testing at about 70 ° C for about four weeks or more.

(1) reacting the pigment (P) with a reactive compound having an XY reactive group and a halogen-containing reagent to form a reactive group XY on the surface of the pigment (P) To form a pigment reactive intermediate (P) XY; And (2) reacting the pigment reactive intermediate (P) X-Y with a secondary compound N-S-ZM to form a self-dispersible pigment (P) -X-S-ZM ("displacement step"). One example of this embodiment includes, but is not limited to, attaching the reactive group X-Y to the surface of the pigment; And thereafter, replacing Y with an organic substrate N-S-ZM to form a surface modified pigment having X-N-S-ZM attached thereto.

In a second embodiment, a process for preparing a self-dispersible pigment (P) -XS-ZM comprises the steps of (1) reacting a reactive compound having an XY reactive group with a second compound NS-ZM to form a substituted reactive intermediate XS-ZM Step ("substitution step"); And (2) reacting the pigment (P) with the substituted reactive intermediate XS-ZM to attach the substituted reactive intermediate XS-ZM to the surface of the pigment using a secondary substitution reaction to form a self-dispersing pigment (P) -XS -ZM. ≪ / RTI > One example of this embodiment includes, but is not limited to, reacting a reactive compound having an X- [Y] n reactive group with a secondary compound NS-ZM to form a substituted reactive intermediate [Y] a -X- b ) < / RTI > And reacting the pigment with a substituted reactive intermediate [Y] a -X- (NS-ZM) b to attach the substituted reactive intermediate to the surface of the pigment to form a surface modified pigment Where n is an integer from 1 to 3, b is an integer from 1 to 3, a = nb, where n is equal to or greater than b and b is 2 or 3, each NS-ZM May be the same or different. In one embodiment, when b is 2 or 3, each NS-ZM may be different.

In a third embodiment, the process for preparing a self-dispersible pigment (P) -XS-ZM comprises the steps of (1) reacting a reactive compound having an XY reactive group with a second compound NS-ZM to form a substituted first reactive intermediate XS- ("Substitution step"); (2) reacting a reactive compound having an X-Y reactive group with a second compound different from step (1) N2-S2-Z2M2 to form a substituted second reactive intermediate X-S2-Z2M2 ("substitution step"); (3) The self-dispersing pigment Z2M2-S2-X- (P) -XS-ZM is prepared by reacting the pigment (P) with the substituted reactive intermediates XS-ZM and X- To form a second layer. Optionally S-ZM and S2-Z2M2 may be the same and all reactive groups will be substituted. The final attachment to the pigment surface can be one of the radical-assisted disproportionation reactions.

In a fourth embodiment, the process for preparing the self-dispersible pigment (P) -X-S-ZM comprises the steps of: (1) milling and dispersing the pigment using a grinding aid to form a pigment water dispersion; (2) reacting a reactive compound having an X-Y reactive group with a second compound N-S-ZM to form a substituted first reactive intermediate X-S-ZM ("substitution step"); (3) Reactive compound having an X-Y reactive group (step "Substitution step") to form a substituted second reactive intermediate X-S2-Z2M2 by reacting with a second compound N2-S2-Z2M2 different from step (2); (4) reacting the substituted reactive intermediates XS-ZM and X-S2-Z2M2 with the pre-milled pigment (P) with the substituted reactive intermediates XS-ZM and X-S2- To form a self-dispersing pigment Z2M2-S2-X- (P) (R) -XS-ZM by attaching it to the surface of the pigment; And (5) purifying the self-dispersing pigment to remove impurities including grinding aids. Optionally, S-ZM and S2-Z2M2 may be the same.

In each of these embodiments, the reactive compound may have an XY reactive group, wherein X may include, but is not limited to, carbonyl, sulfonyl, phosphoryl, cyanuryl, and NH, But are not limited to, acid halide leaving groups including, but not limited to, fluorides, chlorides, bromides, and iodides. In a suitable embodiment, X may be a sulfonyl, phosphoryl or cyanuryl (1,3,5-triazinyl). The acid halide forming reagent contains a halogen. Examples of such reagents include, but are not limited to, chlorosulfonic acid, thionyl chloride, phosphoryl chloride, and combinations thereof. In these compounds, chlorine can be replaced by another halogen. The reactive compound may be stable in the aqueous medium at low temperatures for short durations.

During the substitution step, at least one leaving group Y of the XY reactive group is replaced by a secondary compound NS-ZM, wherein N is a nucleophilic group such as an amine, an imine, a pyridine or a thiol, and S is, Aryl, and polymeric chains having an organic group, such as from about 1 to more than 100 carbons, or a molecular weight ranging from about 300 to about 8000, and in the case of stabilization by negative charge , ZM is an acidic tail group, where Z may be, but is not limited to, carboxyl, sulfonyl, phenolic and phosphoryl, and M is a proton or cationic . Such substitution can impart charge and volume to the surface of the pigment. The displacement step can be carried out in an aqueous medium. The selection of the functional group in the acidic tail is specified according to the final application, but the functional group in the basic head must have nucleophilicity sufficient to displace the leaving group Y. [ The secondary compounds may include polymers, amines, amino acids, alcohols, thiols, and combinations thereof. Examples of secondary compounds and N2-S2-Z2M2 NS-ZM include, but are not limited to, aminobenzoic acid, aminobenzenesulfonic acid, aminophenol, aminosulfonic acid, polyethoxylated amino acid, sodium sulfanilate, , Sodium p-aminobenzoate, p-aminophenol, ethyl 4-aminobenzoate, taurine, oleic acid (amino), sodium aminooleate, tetramethylammonium 4-aminobenzoate and sodium 4-aminophenolate . Additional secondary compounds include organic polymeric substrates. Examples of organic polymeric substrates include, but are not limited to, linear alkyl and branched ethoxy and propoxy chain polymers having a known molecular weight range of 300-3000 MW (available from Huntsman Chemicals under the trade name "Sulfonamines "Quot; Surfonamines "), linear polyethoxy polymer amines, linear propoxy polymer amines, styrene acrylic copolymers (available under the trade designation" Joncryls " from Johnson Polymers) Polyethyleneimine (sold under the trademark "Epomines").

In the case of stabilization by positive charge, ZM may be a positively charged quaternary ammonium type tail, where Z may be, but is not limited to, ammonium, trimethylammonium and tributylammonium, and M is halide Or any negatively charged ions. Examples of the secondary compounds N-S-ZM and N2-S2-Z2M2 include, but are not limited to, simple diamino aromatic or cationic polymers composed of polyethyleneimine, polyguanidine, quaternary ammonium compounds and the like.

The final self-dispersible pigment can be represented by the formula (P) -X-S-ZM for the first and second embodiments. In some instances, there may be multiple-S-ZM attached to a pigment comprising different secondary compounds. For the third embodiment, the resulting self-dispersible pigment may be represented by the formula Z2M2-S2-X- (P) -X-S-ZM. Finally, using "2 " to modify N, Z, M and S means to indicate that N2, Z2, M2 and S2 may be the same or different from N, Z, M and S. N2, Z2, M2 and S2 may be selected from the same options described above for N, Z, M and S.

To illustrate the present invention, specific examples of the first embodiment are provided below, wherein P represents a pigment.

Figure 112010017976960-pct00001

To illustrate the present invention, specific examples of the second embodiment are provided below, wherein P represents a pigment.

Figure 112010017976960-pct00002

To illustrate the invention, specific examples of the third embodiment are provided below, wherein P represents a pigment.

Figure 112010017976960-pct00003

Embodiments of the present invention are discussed in more detail below. Generally, the process for the preparation of the self-dispersing pigment starts with the selection of the pigment source.

Pigment

Pigments that can be surface modified in accordance with the present invention include, but are not limited to, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, thioindigo pigments, triphenylmethane lake pigments and oxazine lake pigments . Specifically, as the pigment having a yellow color, for example, children. Yellow pigment 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 16, 17, 65, 74, 83, 97, 138, 150, 151 and 155. As the pigment having red color, for example, seeds. children. Red pigment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 21, 22, 23, 31, 38, 41, 48, 49, 50, 51, 52, 57, 58, 60, 64, 83, 88, 89, 90, 112, 114, 122, 123, 166, 188, 202, children. Purple pigments 19 and 23 are included. As the pigment having blue color, for example, seeds. children. Blue pigments 1, 2, 15, 15: 3, 15: 4, 16, 25 and 75 are included. As the pigment having green color, for example, children. Green pigments 7 and 36 are included. Examples of pigments having a black color include, for example, children. Black pigments 1 and 7 are included. Commercially available color pigments include, for example, red pigment 122 and purple pigment 19 (Lansco Colors, Montvale, New Jersey or BASF Color, Charlotte, Available from Clariant Colors of Charlotte, Carolina, or Sun Chemical of Cincinnati, Ohio), Blue Pigment 15: 1 (purchased from Fanwood Chemical, Panwood, NJ) (Available from BASF Colors of Charlotte, NC or Clariant Colors of Charlotte, North Carolina) or from Sun Chemicals, Inc. of Cincinnati, Ohio, available from Ciba Specialty Chemicals, Inc., Blue Pigment 15: 3, Blue Pigment 15: 4, Yellow Pigment 74 and Yellow Pigment 97 Available for purchase).

Suitable pigments also include carbon black. Carbon black is a common name for carbon particles derived from pyrolysis or incomplete combustion of natural gas and hydrocarbons (for example aromatic oils, mineral oils, coal tar distillates and acetylenes based on coal tar). More than 100 individual grades of carbon black are currently commercially available, each with its own distinct set of features and characteristics. Any of the acidic carbon black, neutral carbon black and alkali carbon black can be advantageously applied to the process disclosed in the present invention. These include channel black, gas black, lamp black, thermal black, acetylene black and blast furnace black. More specifically, suitable carbon blacks include channel black. The properties of the carbon black used will affect the main properties of the dispersion, such as average particle size, opacity, hue, stability, and the like. Examples of commercially commercially available carbon black include, but are not limited to, Cabot (Cabot) (Elf-Tex (Elftex) 8, black pulse (Black Pearls) ® 490, black pulse ® 120, Monarch (Monarch) ® 120, Monarch ® 700, Monarch ® 880, Monarch ® 1000, Monarch ® 1100, Monarch ® 1300, Monarch ® 1400, mogul (mogul) ® L, Regal (Regal) ® 99R, Regal ® 250R, Regal ® 300R, Regal ® 330R, Regal ® 400R, Regal ® 500R, Regal ® 660R), Degussa (Degussa) (your Pecs (NIPex) ® 150 IQ, you Pecs ® 150, Printex (Printex) ® 55, Printex ® 80, Printex ® 90 , Printex ® A, Printex ® G, Printex ® U, Printex ® V, Printex ® 140U, Printex ® 140V, Pew Rex (Purex) ® LS 35, nose flux (Corax) ® HP 160, thermal black (Thermal black) N 990, you Pécs ® 160 IQ, you Pécs ® 90, Special black (Special black) 4, Special black 4A, Special black 5, Special black 6, Special black 100, Special black 250, color block Rack (Color black) FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, and Color Black S170), kolreombi not (Columbian) (Raven (Raven) ® 780, Raven ® 5000 UII, Raven ® 1255, Raven ® 2500 U, Raven ® 3600 U, Raven ® 3500, Raven ® 7000, Raven ® 1220 and Raven ® 1225) and manufactured by Mitsubishi sikki Chemical right or wrong (Mitsubishi Kagaku KK) (MA8, MA11 # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, # 20, # MA, # MA, MA600, MCF88, # 10B, # 20B, 900, 970 #, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700, # 4000B and CF9.

Pigments can be used in various particle sizes. In general, the smaller the particle size, the larger the surface area, and the larger the surface area, the more hydrophilic surface groups can be accommodated at higher concentrations (which greatly improves the dispersibility of the carbon black in the aqueous-based medium). Thus, the particle size can affect the dispersibility of the surface-modified pigment. For example, in the present invention, the average primary particle size of the carbon black may be less than about 50 nm, especially less than about 30 nm, especially less than about 20 nm, more specifically less than about 10 nm. Aggregates of carbon black particles may be less than about 200 nm, especially less than about 150 nm, more specifically less than about 100 nm. The surface area of the carbon black particles may be greater than about 100 m 2 / g, especially greater than about 150 m 2 / g, more specifically greater than about 200 m 2 / g. Pigment particles with larger dimensions can be ground to a desired size using any of a variety of techniques known to those skilled in the art, either prior to surface modification or during surface modification. These techniques include, but are not limited to, ball mills, rubbing machines, flow jet mixers, impeller mills, colloid mills and sand mills (e.g. under the trade designations "Super Mill", "Agitator Mill), Dyno-mill or Beads Mill, which are commercially available. Mill media include, but are not limited to, glass beads, zirconia beads, and stainless steel beads. Mill media may include particles ranging in size from about 0.1 mm to about 3 mm, more specifically from about 0.01 mm to about 5 mm. If the carbon black is easily broken, the particle size can be reduced by using a rotary homogenizer or an ultrasonic homogenizer. In one embodiment, the surface-modified black pigment is prepared from a commercial grade carbon black pigment having a primary particle size of less than about 30 nm and an aggregate of about 200 nm or less with a surface area of greater than about 100 m 2 / g.

Prior to the preparation of the self-dispersible pigment, the pigment may or may not be oxidized using an oxidizing agent such as nitric acid, ozone, hydrogen peroxide, persulfate, hypohalites, or combinations thereof. The aqueous oxidation of carbon black using sodium hypochlorite is taught by U.S. Patent No. 2,439,442 (issued April 13, 1948) and U.S. Patent No. 3,347,632 (issued October 17, 1967) , Each of which is incorporated herein by reference. After oxidation of the pigment, the compound of formula X-S-ZM is then attached to the surface of the pigment using the method of the present invention to supplement the newly introduced surface charge.

In some instances, prior to the preparation of the self-dispersible pigment, the pigment may be wetted, milled into nanosized particles, and dispersed using a grinding aid. The pigments may be in the form of a powder or wet cake before milling with the aid of a grinding aid. Milling may be effected before, during or after the reaction with the substituted intermediate. After the attachment reaction is complete, the grinding aid can be removed using purification methods known to those skilled in the art, forming a dispersion containing predominantly a modified pigment and water. Examples of grinding aids include, but are not limited to, Triton X-100 (available from Ashland Inc. of Dublin, Ohio), Igepal CA-630 (available from Ashland Inc. of Ohio) (Available from Rhodia, Cranbury, NJ) and Surfynol CT 121, 131 and 141 (available from Air Products, Allentown, Pa.).

In one example of the first embodiment, a reactive compound comprising a sulfonyl chloride is attached to a pigment such as carbon black by chlorosulfonation using chlorosulfonic acid. The combination of acid concentration, reaction temperature and duration determines how many sulfonyl groups are attached to the surface of the pigment. In one embodiment, the chlorosulfonation is carried out using chlorosulfonic acid in an amount that is five times the weight of the carbon black.

Chlorosulfonation can also be carried out using a mixture of chlorosulfonic acid and thionyl chloride to prevent in situ hydrolysis. The amount of thionyl chloride can be very varied to control the degree of hydrolysis or even completely prevent hydrolysis. In one embodiment, the chlorosulfonation is carried out using 348 g of chlorosulfonic acid and 30 g of thionyl chloride.

The ratio of the pigment to the acid (weight ratio) is mainly determined as a function of operational efficiency, including mixing, ease of transport and cost. Chlorosulfonation of the pigment can be achieved by using an excess of chlorosulfonic acid without addition of a solvent. A minimum ratio of the acid to the pigment of about 5 is suitable to provide good mixing throughout the reaction. A very high amount (e.g., a ratio of about 20) increases both the material cost and the handling cost without creating a significant advantage. In one embodiment, the chlorosulfonic acid is used at about 5-fold excess (w / w). In another embodiment, the ratio of pigment to chlorosulfonating agent is at least about 4: 1 (w / w). In another embodiment, the ratio of pigment to chlorosulfonating agent is from about 1: 20 to about 1: 1 (w / w). In a further embodiment, the chlorosulfonating agent may be a mixture of chlorosulfonic acid and thionyl chloride in a ratio of about 3: 1 to about 6: 1 (w / w).

The chlorosulfonation of the pigment can be carried out at elevated temperatures for a period of about 2 days or less. The reaction temperature during the chlorosulfonation may be at least about 140 ° C, in particular at least about 130 ° C, more particularly at least about 120 ° C. In addition, the reaction temperature during the chlorosulfonation can be about 60 캜 or less, particularly about 90 캜 or less, more specifically about 120 캜 or less. This includes embodiments wherein the reaction temperature during the chlorosulfonation is from about 120 캜 to about 130 캜, more specifically about 140 캜 or less. In another embodiment, the reaction temperature during the chlorosulfonation is from about 25 캜 to about 160 캜. In general, the higher the temperature, the shorter the reaction time is required to achieve the desired concentration of the sulfonyl group on the surface of the pigment. For example, the desired chlorosulfonation at a reaction temperature of 140 占 폚 may take about 6 hours, but the same degree of chlorosulfonation at 80 占 폚 is expected to take over 72 hours. In some embodiments, the reaction time may be at least about 2 hours, in other embodiments at least about 6 hours, in yet another embodiment at least about 24 hours. In other embodiments, the reaction time may be up to about 48 hours, in other embodiments up to about 24 hours, in another embodiment up to about 6 hours. This includes embodiments wherein the reaction time is from about 1 hour to about 48 hours. The contents of the reaction vessel are stirred during chlorosulfonation to ensure proper mixing.

After the chlorosulfonation, the reaction mixture can be quenched into water. In some embodiments, the reaction mixture may be quenched after cooling to a temperature of less than about 20 占 폚, and in other embodiments may be quenched after cooling to a temperature of less than about 60 占 폚; in another embodiment, Lt; / RTI &gt; and then quenched. This includes embodiments wherein the reaction mixture is quenched after cooling to a temperature of from about 20 [deg.] C to about 90 [deg.] C. The water to which the reaction mixture is added can be at or below about 10 캜 using, for example, ice, a cooling device, or a combination thereof. In one embodiment, the quenching temperature is maintained at about 0 캜 to about 5 캜 to preserve the reactive sulfonyl chloride intermediate. The chlorosulfonated product (referred to as wet cake) can be isolated from the water by filtration and washed to remove excess reactants and water-soluble products. It can be washed with <5 ° C water.

The pigment reactive intermediate is then substituted with one or more secondary compounds comprising an organic group that prevents it from being hydrolyzed back to the acid. In one embodiment, the pigment reactive intermediate can be used immediately for reaction with the secondary compound. For example, carbon black having a reactive sulfonyl chloride group can react immediately with organic compounds containing amino and acidic end groups. The secondary compound comprising an organic group can be selected according to the desired end application for the pigment.

The pigment reactive intermediate may react with a secondary compound in the acidic pH range (about 2 to about 5). The acidic pH range increases the stability of the reactive compound and reduces the extent of undesirable reactions such as hydrolysis and self-condensation. The reactive compound preferentially reacts with bases such as primary amines even when aminophenols are used as organic groups. Such reactions can be predominantly assigned to the amino terminus by appropriate selection of reaction conditions such as pH, temperature and dilution known to those skilled in the art. For example, the pH may be from about 2 to about 5, and the temperature may be from about 0 캜 to about 5 캜. In another embodiment, during the reaction of the pigment reactive intermediate with the secondary compound, the particle size of the pigment can be reduced by performing the reaction in a bead mill. Since the secondary compound is corrosive, it is possible to select a suitable material of a structure resistant to strong acids and strong bases to prevent metal leaching into the product.

The reaction between the pigment reactive intermediate and the secondary compound may be carried out for a period of from about 2 hours to about 4 hours while mixing. In one embodiment, the reaction can be completed by heating the mixture to an elevated temperature from about 60 캜 to about 90 캜.

Other examples of the first embodiment include, but are not limited to, attaching a reactive group X-Y to the surface of the pigment; And thereafter replacing Y with an organic substrate NS-ZM to form a surface modified pigment with XNS-ZM attached, wherein X is a sulfonyl, phosphoryl or 1,3,5-triazinyl group; Y is a halogen leaving group, N is a basic nucleophilic group, S is an organic group, and ZM is an ionizing end group). Most pigment surfaces can be modified to form liquid gels. The liquid gel can then be milled with excess untreated pigment and water to form a stable pigment water dispersion. An example of modifying most pigment surfaces includes, but is not limited to, chlorosulfonating the pigment for at least about one hour at a temperature of at least about 90 캜 to form a chlorosulfonated pigment or pigment sulfonyl chloride .

In one example of the second embodiment, the reactive compound comprising a cyano group is substituted with a secondary compound comprising an organic group. Substituted reactive intermediate -X-S-ZM is then attached to a pigment such as carbon black by using cyanuric chloride. The combination of pH, reaction temperature and duration determines how many glues are attached to the surface of the pigment. In one embodiment, the reaction is carried out using 52 g of cyanuric chloride per 120 g of carbon. In another embodiment, the reaction is carried out using 15 g of cyanuric chloride per 40 g of carbon.

In some embodiments, a slurry of a secondary compound comprising an organic group, cyanuric chloride, water, ice, and base is prepared. The secondary compound comprising an organic group can be selected according to the desired end application for the pigment.

In an example of the third embodiment, the reactive compound comprising a cyano group is substituted with a secondary compound comprising two organic groups which may be the same or different. Substituted two reactive intermediates X-S-ZM and X-S2-Z2M2 are then attached to a pigment such as carbon black by using cyanuric chloride. The combination of pH, reaction temperature and duration determines how many glues are attached to the surface of the pigment. The process may be carried out sequentially by first reacting with a slurry of a secondary compound comprising an organic group, cyanuric chloride, water, ice and base. A second slurry of different secondary compounds comprising organic groups, cyanuric chloride, water, ice, acid and base is used to complete the process.

The ratio of cyanuric chloride to secondary compound is typically determined by stoichiometry and the concentration is controlled to allow good mixing. The reaction between the cyanuric chloride and the secondary compound can be carried out for a period of from about 2 hours to about 4 hours while mixing.

In one example of the fourth embodiment, by manipulating all of the reactive chlorine in the cyanuric chloride with stoichiometry (three equivalents to replace all three chlorines) and temperature (temperatures above about 90 占 폚) Substituted with a mixture, and then reacted with the pigment. This reaction forms a substituted triazine, and the substituted triazine can be attached to the surface of the pigment. The mixture of secondary compounds may comprise one, two or three different secondary compounds. In this example, a radical initiator such as a persulfate moiety is used to disproportionate and facilitate the attachment method. In some embodiments, the reaction may be carried out at a temperature from about 25 [deg.] C to about 90 [deg.] C. In another embodiment, the pigment can be milled to less than about 100 nm before, during, or after the reaction of the substituted triazine with the pigment.

The pigment is mixed with this "reagent" to produce a dispersion. In embodiments where there are two slurries containing different secondary compounds, the pigments are sequentially mixed with the slurry. The temperature of the dispersion can be maintained at about 0 캜 to about 15 캜 for a period of about 1 hour to about 2 hours. The mixture of the reactive compound (e.g., substituted triazine) dispersion and the pigment is then heated to elevated temperature for a period of about 2 days or less. A free radical initiator such as potassium persulfate may be added to facilitate the reaction. The reaction temperature may be at least about 40 ° C, in particular at least about 50 ° C, more specifically at least about 60 ° C. In addition, the reaction temperature may be about 90 캜 or less, particularly about 80 캜 or less, more specifically about 60 캜 or less. This includes embodiments wherein the reaction temperature is from about 50 째 C to about 60 째 C, more specifically less than or equal to 90 째 C. In general, temperatures above 50 DEG C are needed to ensure that the free radical initiator is effective. This includes embodiments wherein the reaction time is from about 16 hours to about 24 hours. The contents of the reaction vessel are allowed to stir and mix appropriately during the reaction. The modified pigment can be filtered to remove excess reactants and impurities.

In one embodiment, the reactive compound (e.g., cyanuric chloride) reacts with the secondary compound in the acidic pH range (about 2 to about 5). The acidic pH range increases the stability of the reactive compound and reduces the extent of undesirable reactions such as hydrolysis and self-condensation. The reactive compound preferentially reacts with bases such as primary amines even when aminophenols are used as organic groups. Such reactions can be predominantly assigned to the amino terminus by appropriate selection of reaction conditions such as pH, temperature and dilution known to those skilled in the art. For example, the pH may be from about 2 to about 5, and the temperature may be from about 0 캜 to about 5 캜.

Optionally, the pigment may be reduced in particle size by carrying out the reaction in a bead mill while allowing the pigment to react with the group -X-S-ZM. Since the secondary compound is corrosive, it is possible to select a suitable material of a structure resistant to strong acids and strong bases to prevent metal leaching into the product.

Reaction of the pigment with a secondary or reactive compound containing an acid derivative can produce an acidic surface group that can lower the pH of the reaction mixture. Decreasing the pH can destabilize the slurry of modified pigment dispersions or reactive compounds and secondary compounds during displacement and also increase the viscosity. Thus, the pH can be adjusted before and during replacement with a basic reagent, if necessary. The pH of the reaction mixture during the substitution may be at least about 7, in particular at least about 8, more particularly at least about 9. The pH can be adjusted by any known method in the art, including, for example, addition of a base. Suitable bases include, but are not limited to, alkali hydroxides and calcium-free alkali hydroxide (e.g., NaOH, KOH, LiOH, NH 4 OH), alkali carbonate and bicarbonate (e.g., NaHCO 3, KHCO 3 ) And organic bases (e.g., dimethylethanolamine and triethanolamine). In particular, a suitable pH adjusting agent is calcium-free sodium hydroxide.

Surface modified pigment

After completion of the reaction described above, the self-dispersible pigment may be isolated as a dry powder from the reaction mixture. The resulting modified pigment can be purified using a number of techniques known to those skilled in the art to remove unreacted raw materials, by-product salts, and other reactive impurities. Purification techniques may include, but are not limited to, filtration, centrifugation, or a combination of the two. The modified pigment may also be isolated, for example by evaporation, or it may be recovered by filtration and drying using techniques known to those skilled in the art.

Alternatively, the self-dispersible pigment may be delivered as a concentrated aqueous pigment dispersion. The dispersion of the self-dispersible pigment of the present invention can be purified to remove organic and inorganic impurities and other undesirable free species that may coexist in the dispersion as a result of the manufacturing process. Purification techniques may include, but are not limited to, water washing, reverse osmosis and ultrafiltration. In some embodiments, the dissolved impurities are removed by ultrafiltration until the chloride and sulfate content of the 10% solids adjusted feed sample is less than about 150 ppm, especially less than about 100 ppm, and more specifically less than about 25 ppm. . If desired, the pH of the dispersion can be adjusted prior to purification. A sufficient amount of acid or base can be added to adjust the pH of the dispersion to about 7 or higher, especially about 8 or higher, more specifically about 9 or higher. The present invention includes embodiments wherein the pH of the dispersion is from about 7 to about 9. The dispersion may be concentrated by removing a portion of the water if desired. In some embodiments, the dispersion is concentrated to at least about 8% solids, in other embodiments at least about 14% solids, and in other embodiments at least about 20% solids. The present invention includes embodiments wherein the dispersion is concentrated to about 8% to about 16% solids. In another embodiment, the dispersion is concentrated to at least about 10% solids, in other embodiments at least about 18% solids, and in another embodiment at least about 20% solids. The present invention encompasses embodiments wherein the dispersion is concentrated to about 14% to about 8% solids.

In addition, a biocide may be added to the dispersion to inhibit the growth of microorganisms. Examples of suitable biocides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazoline- -Methyl isothiazolinone, and chloromethyl isothiazolinone. &Lt; / RTI &gt; Is a commercially available biocide from Proxel (Proxel) ® CRL, Proxel ® BDN, Proxel ® GXL, Proxel ® XL-2 and Proxel ® TN (George Arch Chemicals of very Smyrna material's (Arch Chemicals) retrieving possible), and X is included Savings establishments (XBINX) ® (PMC Special Tees group of Cincinnati, Ohio, Inc.. (PMC Specialties group, Inc.) obtained from the available). Typically, small amounts of biocides, such as 0.05 to 5 wt%, especially 0.1 to 1 wt%, more particularly 0.2 to 0.4 wt%, of the biocide are used in the dispersion. The present invention comprises 0.3% by weight of biocide.

Agents can also be added to impart fluidity and stability to the dispersion. Examples of such agents are described in U.S. Patent No. 5,059,248 (issued October 22, 1991), U.S. Patent No. 5,591,455 (issued January 7, 1997) and U.S. Patent No. 5,595,592 Issued on May 21) (each of which is incorporated herein by reference). Examples include, but are not limited to, linear aliphatic substituted glycine compounds and salts thereof. As used herein, the term "linear aliphatic substituted glycine" refers to a glycine compound in which the amino group of the glycine is substituted with a linear aliphatic group. Examples of this type of agent that can be used in the practice of the present invention include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, iminodiacetic acid, and Ethanol diglycine and an alkali metal (for example, sodium), an alkaline earth metal (for example, calcium), and an ammonium salt thereof. Other similar linear aliphatically substituted glycine compounds and salts thereof known to those skilled in the art may also be used. In some embodiments, the above-mentioned salts of ethylenediaminetetraacetic acid are used due to their effectiveness, cost effectiveness and non-toxicity. In some embodiments, these agents may constitute from about 0.5 to 3.5% by weight, preferably from about 1.5 to 2.5% by weight of the pigment in the dispersion composition.

The dispersion may optionally be filtered through a filter cartridge for a specified end use of the dispersion. In some embodiments, the filter cartridge has a nominal pore size of about 5 占 퐉 or less, particularly about 1 占 퐉 or less, particularly about 0.5 占 퐉 or less, more specifically about 0.2 占 퐉 or less.

In addition to powders and dispersions, self-dispersible pigments may also be isolated as a wet cake wet pressed cake. In the form of a press cake, the self-dispersible pigment does not aggregate to the dry form and therefore the self-dispersible pigment does not require such as pulverization in use (e.g. in the manufacture of ink).

If desired, the charge-balancing counterion associated with the surface-reforming agent as a result of the attachment / substitution process can be at least partially converted to an acid by use of known ion-exchange techniques such as ultrafiltration, reverse osmosis, Or may be exchanged using a suitable base or salt form, or exchanged or substituted with other suitable cations. Examples of counterions include alkali metal ions (e.g. Na + , K + and Li + ), NR 1 R 2 R 3 H + , wherein R 1 , R 2 and R 3 are independently H, or can be C 1 -C 5 alkyl date which may be substituted), and a combination thereof (e.g., tetraethyl ammonium ion (TEA), tetramethylammonium ion (TMA), ethanol ammonium ion, a triethanol ammonium ion, tetrabutyl Ammonium ions, and the like).

Properties of modified pigments

The self-dispersible pigment may exhibit at least one of long-term and high-temperature stability, higher waterfastness and high writer fastness as compared to that expected in pigment particles with sulfonic acid or carboxylic acid groups, Has a particle size distribution suitable for use in application.

The self-dispersible pigment may have the following properties. The solids ratio (%) of the modified pigment may be from about 8 to about 16.

The pH of the modified pigment dispersion may be from about 5 to about 10.

The viscosity of the modified pigment dispersion may be from about 1 to about 10 cps, especially from about 1.3 to about 7.6 cps.

The surface tension of the modified pigment dispersion may be from about 39 to about 72 dyne / cm.

The amount of Na and K in the modified pigment dispersion may be a measure of the newly attached anionic substrate (sulfanilic acid, or 4-aminophenol or 4-aminobenzoic acid as Na / K form). The amount of Na can be about 100 to about 6500 ppm, and the amount of K can be about 30 to about 1200 ppm.

The increase in the S content in the modified pigment dispersion may be due to the introduction of a sulfonyl group and / or the attachment of a sulfonated substrate such as, but not limited to, sulfanilic acid. The amount of S in the modified pigment may be from about 50 ppm to about 2600 ppm. In one embodiment, the amount of S in the modified pigment may be about 50 ppm for 4-aminobenzoic acid and 4-aminophenol attachment. In another embodiment, the amount of S in the modified pigment can be about 1700 ppm when the sulfanilic acid is attached to the pigment through a sulfone bond.

Application of modified pigments

The self-dispersible pigments according to the invention can be used in numerous end-use applications. These applications include, but are not limited to, coatings, paints, paper, adhesives, latex, toners, fabrics, fibers, plastics and inks. Specific examples include, but are not limited to, printing inks for paper, textiles, fibers, metal decor and plastics, wood stains, recording equipment, and color filters. In particular, the self-dispersing pigments prepared by the process of the present invention are well suited for use in printing applications and wood stains. In one embodiment, inkjet inks incorporating the pigments of the present invention may be useful for high quality printing in inkjet photo printers.

One aspect of the invention relates to an inkjet ink formulation using the self-dispersible pigment described above. The inkjet formulation containing the pigment may perform one or more of the following: 1) provide a uniform, blur-free image at high resolution and density at high density on a print medium; 2) does not cause nozzle clogging, which typically occurs due to ink drying at the nozzle end; 3) rapid drying on paper; 4) good light fastness and water fastness; 5) good long term storage stability; 6) Independent printing characteristics of paper.

The ink composition of the present invention can be prepared by combining the modified pigment with an aqueous vehicle and any suitable additives. The amount (weight ratio) of the modified pigment in the ink composition is at least about 0.1%, especially at least about 10%, more particularly at least about 20%. In addition, the amount (weight ratio) of the modified pigment in the ink composition is about 12% or less, especially about 8% or less, more specifically about 5% or less. The present invention includes embodiments where the amount (weight ratio) of the modified pigment in the ink composition is present in an amount ranging from about 2% to about 12%.

The aqueous vehicle may comprise water, or it may comprise one or more water-soluble organic solvents with water. The water-soluble organic solvent may be combined with water to form an aqueous vehicle. Water-soluble organic solvents include alcohols, polyhydric alcohols such as ethylene glycol, ketones and ketone alcohols such as acetone and diacetone alcohols, ethers such as tetrahydrofuran and dioxane, lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl Sulfur-containing solvents such as thiodiethanol, sugars and derivatives thereof such as glucose, glycerin and oxyethylene adducts of glycerin, and di- An oxyethylene adduct of glycerin may be included. The water-soluble organic solvent may be used alone or in combination. When a mixture of water and a water-soluble organic solvent is used, the amount (weight ratio) of the water-soluble organic solvent in the ink composition is about 5% or more, particularly about 15% or more, and more specifically about 25% or more. The amount (weight ratio) of the water-soluble organic solvent in the ink composition is about 50% or less, particularly about 30% or less, more specifically about 15% or less. The present invention includes embodiments wherein the amount (weight ratio) of the water soluble organic solvent in the ink composition is from about 5% to about 30%. The amount of water in the ink composition is at least about 40%, especially at least about 50%, more particularly at least about 60%. In addition, the amount (weight ratio) of water in the ink composition is about 90% or less, especially about 80% or less, more specifically about 70% or less. The present invention includes embodiments wherein the amount (weight ratio) of water in the ink composition is from 40% to about 80%.

The additives can be used to meet a number of desired properties, such as the requirements of an ink jet printer, or to provide ink stability, light stability, smear resistance, viscosity, surface tension, coating penetration, optical density, adhesion, high lighter resistance or crust resistance &Lt; / RTI &gt; may be introduced into the aqueous vehicle to impart properties that may be needed to provide a balance of &lt; RTI ID = 0.0 &gt; Penetrating agents may be added, for example, to reduce bleed, improve wetting of the print media, or otherwise improve the overall performance of the printed image. Examples of penetrating agents include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, glycol ethers such as ethylene glycol monomethyl ether, diols such as 1,2-alkyldiols, formamides, acetamides, dimethylsulfoxide, sorbitol and But are not limited to, sulfolane. The penetrants may be used alone or in combination. The amount (weight ratio) of the penetrating agent in the ink composition ranges from 0% to about 60%, especially from about 2% to about 40%, more specifically from about 5% to about 20%. The present invention includes embodiments wherein the amount (weight ratio) of the penetrating agent in the ink composition is in the range of from about 10% to about 15%.

The surfactant may be added to the aqueous medium to reduce the surface tension of the ink composition. The surfactant may be an anionic surfactant, a non-ionic surfactant, and / or a cationic surfactant. Suitable surfactants include those described below and those disclosed in U.S. Patent No. 5,116,409 (issued May 26, 1992), U.S. Patent No. 5,861,447 (issued January 19, 1999), and U.S. Patent No. 6,849,111 (Issued on February 1, 2005), each of which is incorporated herein by reference.

Surfactants various trade names is well known, for example, Pluronic (PLURONIC) ® series (NJ, BASF Corporation, eight o'clock petticoat material (BASF Corporation)), Tetronic (TETRONIC) ® series (NJ, BASF Corporation, eight o'clock petticoat material) Al quad (ARQUAD) ® series (Akzo Chemical Inc., Chicago, Illinois. (Akzo Chemical Inc.)), Triton (TRITON) ® series (Union carbide Corporation (Union carbide Corp.) in Danbury, Conn material) standing reportage Nick (SURFONIC) ® series (Note Texaco Chemical Company of Houston, Texas (Texaco Chemical Company)), etoposide quad (ETHOQUAD) ® series (Akzo of Chicago material Chemical Inc.), Armin (ARMEEN) ® series (Akzo Chemicals Inc. of Chicago, Illinois), playing Ico (ICONOL) ® series (BASF Corporation, New Jersey, eight o'clock Trapani material), Management Interviews pinol (SURFYNOL) ® series (fan Banish Air Products and Chemicals of Allentown material's very, Inc.. (Air Products and Chemicals, Inc. )) and Etoile Min (ETHOMEEN) ® Series (available commercially under the Akzo Chemicals Inc.) in Chicago, Illinois have.

Surfactants may be used alone or in combination. The amount (weight ratio) of the surfactant in the ink composition may range from 0% to about 10%, especially from about 0.1% to about 10%, more specifically from about 0.3% to about 5%. The present invention includes embodiments in which the amount (weight ratio) of the surfactant in the ink composition can range from about 0.1% to about 8%.

One or more wetting agents may be added to the aqueous vehicle to prevent clogging of the inkjet nozzles that may occur during latent periods of drying. The wetting agent can be selected from materials having high water absorption and water solubility. Examples of wetting agents include polyols such as glycerol, lactam such as 2-pyrrolidone, urea compounds such as urea, 1,3-dimethylimidazolidinone, saccharides such as sorbitol, 1,4-cyclohexanedimethanol, 1- Methyl-2-piperidone, N-ethylacetamide, 3-amino-1,2-propanediol, ethylene carbonate; Butyryl acetone, and Liponic EG-1. The amount of the wetting agent to be used is not particularly limited, but the amount (weight ratio) of the wetting agent in the ink composition may generally be in the range of 0% to about 30%, particularly about 1% to about 15%, more specifically about 5% have.

The polymer may be added to the ink composition to improve the water-fastness, friction and high lighter fastness of the image on the print medium. Suitable polymers include, but are not limited to, polyvinyl alcohols, polyesters, polyester melamines, styrene-acrylic acid copolymers, styrene-maleic acid copolymers, styrene-maleic-alkyl acrylate copolymers, styrene-methacrylic acid copolymers, But are not limited to, acid-alkyl acrylate copolymers, styrene-maleic acid hard ester copolymers, vinyl-naphthalene-acrylic acid copolymers, vinyl naphthalene-maleic acid copolymers and salts thereof. The amount (weight ratio) of the polymer in the ink composition may range from 0% to about 5%, especially from about 0.1% to about 3%, more specifically from about 0.2% to about 2.5%. The present invention includes embodiments wherein the amount (weight ratio) of the polymer in the ink composition may range from about 0.1% to about 3.0%.

The ink composition of the present invention can be buffered to a desired pH using various pH adjusting agents. Suitable pH adjusting agents may include alkali hydroxides, alkaline carbonates and bicarbonates, triethylamine, dimethylethanolamine, triethanolamine, mineral acids, hydrochloric acid and sulfuric acid. The pH adjusting agent may be used alone or in combination. The amount (weight ratio) of the pH adjusting agent in the ink composition may range from 0% to about 3.0%, especially from about 0.1% to about 2.0%, more specifically from about 0.5% to about 1.5%. The present invention includes embodiments wherein the amount (weight ratio) of the pH adjusting agent in the ink composition ranges from about 0.2% to about 2.5%.

Preservatives, such as biocides and fungicides, may also be added to the ink composition. Examples of suitable preservatives include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazoline- Methyl isothiazolinone, and chloromethyl isothiazolinone. Commercially available biocides include Wu carboxylic seed (UCARCIDE) ® 250 (available from Union Carbide Company, are possible), Proxel ® CRL, Proxel ® BDN, Proxel ® GXL, Proxel ® XL-2, Proxel ® TN (available from Arch Chemical's of Georgia Smyrna material available), dawooyi Siege (Dowicides) ® (MI Dow Chemical Company of Midland (Dow Chemical)), nyuoh septeu (Nuosept) ® (NJ piece Kita way hwilseu material Americas , Inc.. (Huls America, Inc.)) , Omi dinjeu (Omidines) ® (De Corporation of Cheshire, Conn material (Olin Corp.)), Nopco Siege (Nopcocides) ® (Henkel paensil Vanity very Ambler material Corporation (Henkel Corp.)), Troy Sans (Troysans) ® (Troy Chemical Corp. of Newark, NJ material (Troy Chemical Corp.)) and X Savings establishments ® (Ohio, including the PMC Special Tees group, Inc. of Cincinnati,) do. Preservatives may be used alone or in combination. The amount (by weight) of preservative in the ink composition may range from 0% to about 1.5%, especially from about 0.05% to about 1.0%, more specifically from about 0.1% to about 0.3%. The present invention includes embodiments wherein the amount (weight ratio) of the preservative in the ink composition may range from about 0.05% to about 0.5%.

The ink composition may contain one or more viscosity modifiers. The viscosity adjusting agent may include a rosin compound, an alginic acid compound, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, salts of polyacrylic acid, polyvinyl pyrrolidone, gum arabic and starch. The amount (weight ratio) of the viscosity modifier in the ink composition may range from 0% to about 10%, especially from about 0.5% to about 8%, more specifically from about 1% to about 5%. The present invention includes embodiments wherein the amount (weight ratio) of the viscosity modifier in the ink composition may range from about 1% to about 7%.

Other additives that may be introduced into the aqueous vehicle also include antioxidants, ultraviolet absorbers, chelating agents, electrical conductivity modifiers, viscosity modifiers, oxygen sorbents, kogation agents, anti-curling agents, Anti-foaming agents, and buffering agents. The ink composition of the present invention may also contain at least one coloring agent in addition to the pigment dispersion of the present invention.

The ink composition of the present invention is particularly suitable for use as an ink composition for inkjet printing in which a droplet of the ink composition is ejected from the printing equipment and deposited on the substrate to produce an image. Suitable printing equipment includes continuous ink jet (CIJ), drop-on-demand valves (DoD valves), drop-on-demand piezo-electric (DoD piezo And Thermal Ink Jet (TIJ). &Lt; / RTI &gt; Similarly, any suitable substrate can be used including plain paper, bond paper, coated paper, transparencies, fabrics, plastics, polymer films and inorganic substrates. However, those skilled in the art should appreciate that the ink composition may also be used in other applications including, but not limited to, conventional recorder application and stamp application.

The ink composition of the present invention may be used alone or in combination with a color underlay to produce a black image, or may be used with other ink compositions to produce a color image. In some embodiments, the ink composition of the present invention is used with other ink composition (s) such as cyan ink, magenta ink and / or yellow ink. In another embodiment, the cyan ink, the magenta ink, and the yellow ink are overprinted to form a black image, which is used in conjunction with the printing of the black ink of the present invention.

Wood stain

Another aspect of the invention relates to aqueous formulations using the self-dispersing pigments described above as wood stains and coatings. Wood stain formulations containing such pigments may exhibit one or more of the following properties: 1) Good wood absorbency and adhesion; 2) Good transparency; And 3) excellent water and light resistance.

The water resistance is determined by the difference in the measured DE * value of the wood stain of the control versus the control area. Low DE * values can indicate high water resistance. If DE * is small, it may mean that there is minimal or no color change due to decomposition or loss. For example, a low DE * value can indicate a high water resistance as shown in a carboxy modified pigment dispersion. The DE * value of the modified pigment dispersion may be from about 0 to about 3. One particular example is a pigment modified with 4-aminobenzoic acid. In another embodiment, the carboxy modified Blue Pigment 15 and Yellow Pigment 74 dispersions had low DE * values of about 0.19 and 0.43, respectively. Delta E is the difference between the two colors. The L, a, and b values are measurements based on a spherical color. + L = white, -L = black, + a = red, -a = green, + b = yellow, -b = blue. C is chromaticity (saturation), and H is color. The reading is measured using a spectrophotometer.

Figure 112010017976960-pct00004

coating

Coating formulations containing such pigments can exhibit one or more of the following properties: 1) Good adhesion to substrates, such as metals, paper, glass, plastic and wood; 2) ease of application and drying; 3) Good weather fastness, water and light resistance; 4) Good gloss retention; And 5) good chemical resistance and flocculation resistance.

As with water tolerance, the resistance of the coating to strong acids and strong bases is measured by the difference in the DE * value of the spotted area versus the control. The DE * value of the modified pigment dispersion may be from about 0 to about 3. In one embodiment, the coating containing the modified carbon black had a low DE * value of about 0.08 against acid tolerance. In another embodiment, the coating containing modified blue pigment 15 had a low DE * value of about 1.56 for resistance to strong bases.

Color filter

Another aspect of the invention is an aqueous formulation using the self-dispersible pigment described above in a color filter. The application of color filters is found in the field of display imaging, including, but not limited to, desktop monitor / laptop screens, LCD TV screens, mobile phone display panels, digital camera screens and GPS panels. Color filter formulations containing the pigments of the present invention may exhibit one or more of the following properties: 1) Good adhesion to glass and plastic film substrates; 2) Good transparency; 3) ease of application and drying; And 4) good heat and light resistance.

The transmissivity of a particular color filter is measured to determine its usefulness. Color filters have maximum transmittance in a narrow band and can provide maximum efficacy.

In one embodiment, the carbon black may not have a transmission band, the magnet pigment dispersion may have the lowest transmission in the range of about 520 to about 560 nm, and the yellow pigment dispersion may have an impurity in the range of about 400 to about 480 nm And the cyan pigment dispersion may have the lowest transmission in the range of about 600 to about 680 nm.

Textile printing

Another aspect of the invention is an aqueous formulation using the self-dispersible pigment described above in fabric printing applications. The textile printing formulations containing the pigments of the present invention may exhibit one or more of the following properties: 1) Good adhesion to fabrics such as cotton fabrics, nylons, polyester, wool, polyacrylic, or blends thereof; 2) ease of application and drying; 3) good water and light resistance; And 4) good wash fastness.

The fastness to washing and water fastness properties of the colored fabrics can be measured by the difference of the DE * value of the fabric versus the washed fabric.

The DE * value of the modified pigment dispersion may be from about 0 to about 3. In one embodiment, the modified carbon black may have a low DE * value of about 0.23. In another embodiment, the modified yellow pigment 74 may have a high DE * value of about 6.72.

Example

Exemplary embodiments of the invention are provided in the following examples. The following examples are presented to illustrate the invention and to aid those skilled in the art in making and using the invention. The embodiments are not intended to otherwise limit the scope of the invention in any way.

Example 1

Pigment dispersion (an example of small molecule attachment after chlorosulfonation in chlorosulfonic acid and thionyl chloride).

Gaseous carbon black (65 g), commercially available from Degussa (Burrridge, IL), having a primary particle size of 20 nm and a BET surface area of 160 m 2 / g, was mixed with 332 g of lab grade chlorosulfonic acid Lt; / RTI &gt; The reaction mixture was cooled to 56 [deg.] C and 68.5 g of thionyl chloride was added dropwise. After all of the thionyl chloride was added, the reaction mass was heated again to 103-5 캜 and held at that temperature for 4 hours. The reaction mixture was then cooled to room temperature and quenched with water and ice while controlling the quenching temperature to below -5 &lt; 0 &gt; C. The precipitated product was isolated by filtration and washed with ice cold water (<5 ° C) to free the dissolved material. The product cake (253 g) was then added to a solution of ethyl 4-aminobenzoate (laboratory grade, Aldrich, 21.7 g) in 140 g deionized water containing 15.5 g concentrated hydrochloric acid (37% &Lt; / RTI &gt; After mixing for 30 minutes at 2000 rpm, it was mixed with 0.4 mm YTZ media (available from Quackenbush Co., Inc., Crystal Lake, Ill.) At 5000 rpm, Hockmeyer media mill (available from Hockmeyer Equipment Corp., Elizabeth City, Calif.) To raise the temperature to 10 ° C and to pH 4.7 with the addition of 20% sodium acetate solution . The milling was continued for another 5 hours. One hour after the milling, the pH was raised to 12.6 by the addition of calcium-free sodium hydroxide (23 g). The reaction mixture was removed from the mill and heated to 85 [deg.] C for 2 hours to hydrolyze the methyl ester. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 18% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Smyrna, GA). Finally, the product was filtered through a 0.7 탆 GF filter.

Examples 2-9

Example 2-9 was prepared according to the same method as described for Example 1 above.

Figure 112010017976960-pct00005

1 Degussa (Burridge, Illinois)

2 PB15: 4 from CIBA (Newport, Del.)

3 PB 15: 3 from BASF (Mount Olive, NJ), and the larger particles were separated by centrifugation at 10,000 rpm for 5 minutes before filtration with 0.7 μm TCLP.

4 PB15: 3 from Clariant Colors (Charlotte, North Carolina)

[Table 1 Continued]

Figure 112010017976960-pct00006

In the first half of the Examples, abbreviations were used for brevity. "H" represents time, "AP" represents aminophenol, "SA" represents sulfanilic acid, and "4ABA" represents 4-aminobenzoic acid.

Example 10

Pigment dispersion (an example of the formation of different salt forms via attachment - for example, tetramethylammonium salts).

Gaseous carbon black (66 g) commercially available from Degussa, with a primary particle size of 20 nm and a BET surface area of 160 m 2 / g, was chlorosulfonized with 348 g of laboratory grade chlorosulfonic acid at 122-7 ° C for 19 hours . The reaction mixture was cooled to 74 DEG C and 30.0 g of thionyl chloride was added dropwise. After all the thionyl chloride was added, the reaction mass was heated again to 134 ° C and held at this temperature for 1 hour. The reaction mixture was then cooled to room temperature and quenched with water and ice while controlling the quenching temperature to below -5 < 0 &gt; C. The precipitated product was isolated by filtration and washed with ice cold water (<5 ° C) to free the dissolved material. The product cake (326 g) was then mixed in ice-cold deionized water to obtain a slurry having pH = 1.5. The pH was initially raised to 4.5 with tetramethyl ammonium hydroxide solution (25%). 90 g deionized water containing 25.0 g of tetramethylammonium hydroxide solution (25%) and 40 g of Surfinol CT-141 (available from Air Products and Chemicals, Inc., Allentown, Pancylone, The pH was further raised to 6.5 with a solution of 4-aminobenzoic acid (laboratory grade, Aldrich, 18 g). This was then mixed briefly with additional tetramethyl ammonium hydroxide solution (25%) and a final pH of 9.6. The mixture was cooled to 4 DEG C and then pelletized using a 0.4 mm YTZ media at 4800 rpm (available from Quark &amp; Co., Inc., Crystal Lake, Ill.) In a Brookhaven media mill Available from Meyer Equipment Corporation) to raise the temperature to 37 DEG C and to control the pH to greater than 8.8 by addition of the tetramethyl ammonium hydroxide solution. The milling was continued for a total of 4 hours. The reaction mixture was removed from the mill and heated to 60-76 [deg.] C for 15 hours. Additional tetramethyl ammonium hydroxide was added to raise the pH to 9.2. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 17% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, a portion of the product (112 g) was filtered through a 0.7 탆 GF filter.

Example 11

Pigment dispersion (chlorosulfonation of PB15 in chlorosulfonic acid; attachment with sulfanilic acid and examples of PB15 dispersion).

Blue pigment 15: 1 (60 g), commercially available from Newchemic (Montville, NJ), was chlorosulfonized with 320 g of lab grade chlorosulfonic acid at 110-118 ° C for 1 hour. The reaction mixture was cooled to 25 캜 and quenched in water and ice while controlling the quenching temperature to below 0 캜. The precipitated product was isolated by filtration and washed with ice cold water (<5 ° C) at pH <4 to free the dissolved material. Subsequently, sulfanilic acid (20 g, available from Nation Ford Chemical, Fort Mill, SC) in deionized water (200 g) with good mixing (1100 rpm) of the product cake (365 g) Was added to a solution of Ca-free sodium hydroxide granules (6.4 g) and sodium bicarbonate (21.7 g). The pH was controlled above 8.0 with an additional 37 g sodium bicarbonate and 21 g sodium carbonate. The mixture was then extruded from a Brookhaven media mill (from Brookhaven Material Corporation, Elizabeth City, Calif.) At 4000 rpm using 0.2 mm YTZ media (available from Quark, Inc. of Crystal Lake, Ill. Lt; / RTI &gt; available). The temperature was raised to 80 DEG C and the mixture was milled for 3 hours. The reaction mixture was removed from the mill and heated to 83 &lt; 0 &gt; C. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to about 5% solids to give 1446 g of liquid. A portion of the liquid product (220 g) was used to disperse 40 g of the blue pigment 15: 3 from Clariant Colors (Charlotte, NC) and milled at 7000 rpm for 3 hours. The final pH of the calcium-free sodium hydroxide solution (1.4 g, 25%) was continuously adjusted to above 8. The product was removed from the mill, heated to 86 캜, and once dissolved, the dissolved impurities were removed by ultrafiltration until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to about 12% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Larger particles were removed by centrifugation at 3,200 rpm for 15 minutes and the product (210 g) was filtered through a 0.7 쨉 m GF filter.

Example 12

Pigment dispersion (Example of addition of cyanoery group and attachment of sodium 4-aminobenzoate).

A solution of 4-aminobenzoic acid (40 g), calcium-free sodium hydroxide (14 g) and sodium bicarbonate (52 g) in deionized water (600 g) was added to cyanuric chloride (52 g, Lonza Walker, (Available from Lonza Walkersville, Inc.), ice (880 g) and deionized water (200 g). The pH was raised to 3.1, and the reaction mixture turned into a milky white dispersion.

Prior art processes for the oxidation of carbon black to sodium hypochlorite, described in U.S. Patent No. 3,347,632, were used to oxidize gaseous carbon black (Degussa) with a primary particle size of 20 nm and a BET surface area of 160 m 2 / g. Carbon black slurry (908 g at 11%) was slowly added to the milky white dispersion described above, keeping the temperature at 1-6 [deg.] C. After 1 hour, the reaction mixture was heated to 19 DEG C and the pH was maintained at 7.3 by addition of calcium-free sodium hydroxide (2 g) and sodium bicarbonate (10 g) [Step 1]. After addition of potassium persulfate (63.6 g laboratory grade, available from Fisher Scientific), the reaction mixture was heated to 57-70 [deg.] C for 20 h [Step 2]. After diluting to 3 L, the pH was raised from 5.3 to 10.3 with calcium-free sodium hydroxide (32.3 g). The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 11% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Smyrna, Georgia). Finally, the product (832 g) was filtered through a 0.7 쨉 m GF filter.

Examples 13-21

Examples 13-21 were prepared according to the same procedure as described for Example 12 above. The additional step of footnote 5 corresponds to Example 13 only.

Figure 112010017976960-pct00007

5 Degussa products with a primary particle size of 13 nm and a BET surface area of 320 m 2 / g. After diluting to 3.6 L, the pH was raised from 5.7 to 9.0 with 50% sodium hydroxide (20.3 g). The slurry was filtered hot (90 [deg.] C through a 300 [mu] m bag filter). 30 g of potassium persulfate was added to the carbon slurry previously cooled to room temperature. A solution of 15 g of 4-aminobenzoic acid (15 g), calcium-free sodium hydroxide (5 g) and cyanuric chloride (15.3 g, available from Lonza Walkersville, IN) in deionized water (300 g) and sodium bicarbonate ) Was added to the stirred mixture. Surfinol CT-121 (available from Air Products and Chemicals, Inc., Allentown, PA) was added to control the bubbling. The pH was adjusted to 7.7 with 50% sodium hydroxide solution (5.4 g) and mixed in a high shear mixer for an additional 15 minutes. The temperature was raised above 50 &lt; 0 &gt; C and held for 20 hours. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 11% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Smyrna, Georgia). Finally, the product (736 g) was filtered through a 1.0 [mu] m Whatman Polycap 36 AS filter capsule.

6 PR 122 from Shiva (Newport, Del.)

7 PY 74 from SUN (Parsippany, NJ)

8 Shiba's PB 15: 3

9 SUN's PR 122

[Table 2 Continued]

Figure 112010017976960-pct00008

Example 22

Pigment dispersion (an embodiment of cyanuric addition and attachment of sodium 4-aminobenzoate and an alkyl polymer amine of approximately MW 300).

A solution of 4-aminobenzoic acid (7.4 g), calcium-free sodium hydroxide (2.3 g) and sodium bicarbonate (30 g) in deionized water (200 g) was obtained from cyanuric chloride (10 g, Lonza Walkersville, Available), ice (130 g) and deionized water (40 g). The pH was raised to 5.5, and the reaction mixture turned into a milky white dispersion.

A solution of sulfonamide B30 (8.6 g, available from Huntsman Chemicals, Austin, TX) in deionized water (60 g) containing concentrated hydrochloric acid (3.75 g) at a pH of 1.5 was added to cyanuric chloride , Lonza Walkersville, Inc.), Ice (100 g) and deionized water (30 g). The pH was raised to 2.1, and the reaction mixture turned into a milky white dispersion. While maintaining the temperature cool (5.7 ° C), the pH was gradually raised to 7.1 with 20 g sodium bicarbonate.

The carbon black formed by the sulfonated and oxidized with sulfuric acid and sodium hypochlorite self-dispersed carbon black dispersion (Sensi jet (Sensijet) ® Black SDP 2000, at 14% 500 g, St. Louis, Missouri Sensi gradient color's Inc. of the material, (Available from Sensient Colors Inc) was precooled in an ice box. While maintaining the temperature at 6-13.7 占 폚, the cold milky white dispersion described above was added to the cold carbon black dispersion. After 1 hour, the 4-aminobenzoic acid adduct (10.7 ° C) with the cyanuric chloride prepared above was added while mixing well. The reaction mixture was warmed to 18.8 캜 (pH 7.4) and then 34 g of potassium persulfate was added. Immediately after the above step, the reaction mixture was heated to 51-57 占 폚 for 20 hours (Step 1). After diluting to 2 L, the pH was raised from 7.2 to 10.9 with calcium-free sodium hydroxide (22 g). The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 14.4% solids and mixed with (0.3%, wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, the product (538 g) was filtered through a 0.7 [mu] m GF filter.

Examples 23-25

Examples 23-25 were prepared according to the same procedure as described for Example 22 above.

Figure 112010017976960-pct00009

Shen 10 color gradient's increment (St. Louis, Missouri) Sensi's Jet ® Black SDP 2000

Shen 11 color gradient's increment (St. Louis, Missouri) Sensi's Jet ® Black SDP 1000

Example 26

Pigment dispersions (Examples for the preparation of cyanuric tris adduct (S) using sulfanilic acid and for use in surface modification of pigments).

A solution (pH = 8.5) of sulfanilic acid (114 g), calcium-free sodium hydroxide (32 g) and sodium bicarbonate (55 g) in deionized water (310 g) Was added to a stirred mixture of cyanuric chloride (40.2 g, available from Lonza Walkersville, Inc., Walkersville, Md.), Ice (570 g) and deionized water (480 g) . After addition (pH = 7.1), the reaction mixture was heated to 90 DEG C over 4.5 hours to give 1000 g of a clear liquid.

Carbon Black 12 (40 g, available from Cabot Corporation, Billerica, Mass.) Having a primary particle size of 16 nm and a CTAB surface area of 255 m 2 / g was mixed with 10.55 g of sulfanilic acid &Lt; / RTI &gt; and 250 g of deionized water. The mixture was transferred to a Brookfield Mill mill using a 0.2 mm YTZ media (available from Quakenbush Campaign, Inc., Crystal Lake, Ill.) As obtained from the Brookhaven media mill (available from Hawkmeier Equipment Corporation, Elizabeth City, Calif.) Lt; / RTI &gt; A solution of 15 g of potassium persulfate and sodium bicarbonate in deionized water was added to the mill and milling was continued for a total of 5 hours. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 11.6% solids and mixed with 0.3% (wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, the product was filtered through a 0.7 탆 GF filter.

Examples 27-38

Examples 27-38 were prepared according to the same procedure as described for example 26 above.

Figure 112010017976960-pct00010

12 Cabot (Cabot; MA Leo Mini master), Monarch (Monarch) ® 880

13 Cabot (Massachusetts, Leo Mini master) Monarch ® 700

Example 39

Pigment dispersion (an example for the preparation of cyanuric tris adducts with 4-aminobenzoic acid and for use in surface modification of pigments).

A solution (pH = 7.2) of 4-aminobenzoic acid (90.1 g), calcium-free sodium hydroxide (30 g) and sodium bicarbonate (55 g) in deionized water (300 g) (40.2 g, available from Lonza Walkersville, Inc., Walkersville, Md.), Ice (550 g) and deionized water (500 g) in three steps controlling the temperature to < . After the addition, pH = 7.1 and the reaction mixture was heated to 92 DEG C over 3 hours to obtain 901 g of a clear liquid.

Carbon black (40 g, available from Degussa, Burridge, Illinois) having a primary particle size of 20 nm and a BET surface area of 160 m 2 / g was mixed with the reagents described above (10.22 g of 4-aminobenzoic acid equivalent ) And 250 g of deionized water. The mixture was transferred to a Brookfield Mill mill using a 0.2 mm YTZ media (available from Quakenbush Campaign, Inc., Crystal Lake, Ill.) As obtained from the Brookhaven media mill (available from Hawkmeier Equipment Corporation, Elizabeth City, Calif.) Lt; / RTI &gt; A solution of 8.5 g of potassium persulfate and sodium bicarbonate in deionized water was added to the mill and milling was continued for a total of 6 hours. The dissolved impurities were removed by ultrafiltration until the chloride and sulfate contents of the feed samples were less than 50 ppm. The product was then concentrated to 10.3% solids and mixed with 0.3% (wt / wt) Proxel GXL (available from Arch Chemicals, Georgia Smyrna). Finally, the product was filtered through a 0.7 탆 GF filter.

Examples 40-47

Examples 40-47 were prepared according to the same procedures as described for Example 39 above.

Figure 112010017976960-pct00011

Example 48

The physical properties of the modified pigment obtained from the above examples are shown in the following table.

Figure 112010017976960-pct00012

Figure 112010017976960-pct00013

[Table 6 Continued]

Figure 112010017976960-pct00014

Figure 112010017976960-pct00015

14 Sum of Ca, Mg and Fe present as contaminants in the raw material and / or formed during the milling process.

Example 49

X-ray photoelectron spectroscopy (XPS) analysis

XPS data were collected and analyzed for black samples 1-5 (Table 7), cyan samples (6-11), magenta samples (12-16), and yellow samples (17-21). Dry samples of the purified "Tris" reagent were also analyzed to characterize the groups attached to the pigment surface.

Figure 112010017976960-pct00016

XPS data was obtained by EAG Laps (Chan Hassen, Minn.) Using a probe beam of concentrated monochromatic Al K alpha emission. X-rays generate photoelectrons, which are analyzed and energized to reveal the atomic composition and chemistry of the sample surface. Optoelectronic escape depth limits the depth of the analysis to about 50 Å outside. The data presented includes low resolution irradiance scans, which provide a full spectrum of binding energy from 0 to 1400 eV. Also included in the data are high-resolution spectra from selective elements providing chemical state information. Using the spectrum, the surface composition was obtained by integrating the area under the photoelectron peak and applying an empirical sensitivity coefficient. The XPS data is shown in FIGS.

Figure 112010017976960-pct00017

Table for carbon black samples

The following table was normalized to 100% of the detected elements. XPS does not detect H or He. The detection limit is typically 0.05% to 1.0% for the other elements. The dash "-" indicates that no element was detected. EXAMPLES [1] [Carbon] High S (0.6) for A-79 is an indicator of surface SO 2 bonding introduced by chlorosulfonation. The high S content in the SA attached examples [20] and [31] is due to the SO 3 Na group present on the surface by SA attachment. Both the unreacted carbon of Example [41] and the 4-ABA attached carbon had only a low level of S as expected. The levels of N and Na present in all samples except for unreacted carbon are measures of the charge groups present as amino benzoic acid or benzenesulfonic acid groups as the corresponding sodium salts.

[Table 9-1]

Figure 112010017976960-pct00018

[Table 9-2]

Figure 112010017976960-pct00019

[Table 9-3]

Figure 112010017976960-pct00020

[Table 9-4]

Figure 112010017976960-pct00021

[Table 9-5]

Figure 112010017976960-pct00022

S present in untreated carbon as sulfide was mostly oxidized with sulfate / sulfone in all treated samples and added to the surface charge.

Table for PB 15 samples

[Table 10-1]

Figure 112010017976960-pct00023

[Table 10-2]

Figure 112010017976960-pct00024

The C-O bond can also contribute to the strength of the band.

[Table 10-3]

Figure 112010017976960-pct00025

[Table 10-4]

Figure 112010017976960-pct00026

Table for PR 122 samples

[Table 11-1]

Figure 112010017976960-pct00027

[Table 11-2]

Figure 112010017976960-pct00028

The C-O bond can also contribute to the strength of the band.

# C 2 NH is the next group:

Figure 112010017976960-pct00029
Lt; RTI ID = 0.0 &gt; C &lt; / RTI &gt;

[Table 11-3]

Figure 112010017976960-pct00030

Table for PY 74 samples

[Table 12-1]

Figure 112010017976960-pct00031

[Table 12-2]

Figure 112010017976960-pct00032

The C-O bond can also contribute to the strength of the band.

[Table 12-3]

Figure 112010017976960-pct00033

[Table 12-4]

Figure 112010017976960-pct00034

The XPS results indicate that a modified carbon black with increased surface nitrogen as the NH / N-C = N group distributed approximately equally at about 0.7 to 2.7 atomic percent with the surface modification as described.

XPS results have surface oxygen with an atomic ratio of about 6.8 to 20.9% with surface modification as disclosed, wherein> 51 to 62% of the oxygen is present as a C = O, COONa, or SOx group and the remainder (49-38% ) &Lt; / RTI &gt; is present as a CO group. Conversely, surface oxygen in untreated carbon black is only about 2.4%, distributed as 32% as C = O, COONa or SOx groups, and the remainder (68%) as C-O groups. SOx can be the oxidized form of S and includes, but is not limited to, sulfone, sulfate, or sulfonic acid.

The XPS results show that the surface modification results in a modified carbon black with increased surface sodium as COONa / SO3Na at about 0.7 to 2.6 at%.

The XPS results indicate that at least 90% of the S present in the surface modification as described is S (SOx) oxidized modified carbon black.

XPS results for untreated carbon black and carbon black from Examples 1, 20, 31, and 41 are shown in FIGS. 1-4.

The XPS results indicate that a modified blue pigment 15 having a significantly higher surface oxygen content (> 2.5% atomic ratio) is obtained compared to the lower 1.6% in the untreated pigments with surface modification as described. The XPS results for the untreated blue pigment 15 and the blue pigment 15 from Examples 7, 9, 11, 16 and 42 are shown in FIGS. 5-7.

The XPS results show that 24-32% of the total O is present as a CO bond, compared to the surface modification as disclosed, where the surface oxygen is 8.3- 9.8% by atomic ratio and only 12% of the untreated pigment is present as CO Lt; RTI ID = 0.0 &gt; 122 &lt; / RTI &gt; The XPS results for untreated red pigment 122 and red pigment 122 from Examples 14, 21, 37, and 45 are shown in FIGS. 8-11.

XPS results, and 21.6 to 29.3%, the surface oxygen to surface modification as disclosed atomic ratio, where also 42-48% of the yield of the modified Pigment Yellow No. 74 is present as a C = O, COONa / CSO 3 Na . In contrast, in the untreated pigment, one merely has surface oxygen only about 20.8%, present as a 41% are C = O, COONa / CSO 3 Na of the group. XPS results for untreated yellow pigment 74 and yellow pigment 74 from Examples 15, 29 and 46 are shown in Figures 12-14.

Example 50

Figure 112010017976960-pct00035

15 Sodium and potassium were calculated from 100% solids from ICP metal analysis of the original dispersion.

[Table 13 Continued]

Figure 112010017976960-pct00036

15 Sodium and potassium were calculated from 100% solids from ICP metal analysis of the original dispersion.

The elemental analysis results show that a surface modification as described yields a modified blue pigment 15 with 0.168-0.430 mMoles of S and 0.070-0.313 mMoles of active hydrogen per gram of pigment.

Elemental analysis results show that a surface modification as described has resulted in a modified red pigment 122 with 0.062-0.187 mM S of S and 0.077-0.394 mMole of active hydrogen per gram of pigment.

The elemental analysis results show that a surface modification as described results in a modified yellow pigment 74 having 0.131-0.178 mMoles of S and 0.192-0.290 mMoles of active hydrogen per gram of pigment.

The elemental analysis results show that the surface modification as described has resulted in a modified carbon black with 0.103-0.702 mMole of S and 0.203-1.579 mMole active hydrogen per g of pigment.

Example 51

Measurement of particle size and stability

Samples containing 8-15% solids were prepared by diluting sample 1 droplets in 15 ml deionized water and loading into a 1 cm disposable cuvette avoiding air bubbles. Subsequently, the median particle size in the sample was measured using a Malvern Zetasizer Nano series model ZEN3600.

Figure 112010017976960-pct00037

Examples 52-55

Print performance - Print test with Epson C88 + printer

A total of three ink sets were prepared. The first set (SA3) consisted of the inks prepared as described below with dispersions prepared by attachment of sulfanilic acid (SA). The second and third ink sets BA3 and BA were prepared using 4-aminobenzoic acid (4-ABA) attached pigment. Using the Epson C88 + printer model B251A, which is known to use pigmented ink sets, a test page was printed with four different commonly used copy papers. The printed pages were analyzed at an integrated production center at Rochester Institute of Technology (Rochester, NY). The results are shown in Tables 17 and 20-22.

Example 52

The following ink base was prepared according to the procedure described below and used to prepare the final ink with a black dispersion.

Figure 112010017976960-pct00038

First, 9.6% by weight of water was added to a clean vessel. The mixing device was then placed in the vessel to shake the water and to provide mixing while adding the other ingredients. Mixing was performed using a magnetic stirrer. Then, 10% by weight of 2-pyrrolidone, 5% by weight of 1,5-pentanediol, 4% by weight of PEG 600 and 1% by weight of 1,2-hexanediol were added to the vessel. This was dissolved. Subsequently, 0.1% by weight of a solution of Surpinol 104E and 0.3% by weight of Nipacide BIT 20 were added and dissolved.

Example 53

The following inks were prepared according to the procedure described below.

Figure 112010017976960-pct00039

A second vessel was prepared by adding the calculated weight percent deionized water to the vessel according to Table 16 for the pigment dispersion. Subsequently, the magnetic stirring apparatus was placed in the vessel. Next, an ink base, followed by a surpinol surfactant (available from Air Products and Chemicals, Inc., Allentown, PA) was slowly added to the pigment dispersion in the second vessel. The dispersion was mixed during this process. After all the diluents have been added, the ink is mixed for about 1 hour or until completely homogeneous. After mixing, the ink was filtered using a 1 [mu] m glass filter (available from Watman, Kent, England).

The printing performance characteristics of the black ink were confirmed as follows.

Image quality was measured by Image Expert Full Motion System (ImageXpert Full Motion System). The optical density was measured with an X-rite 939 spectrophotometer. Ozone exposure was measured using a RIT custom ozone chamber and the Sutherland Rub test was performed with a Southern Land rubbing facility. The RIT supplied a printed page identified as an ink set and media. A yellow highlighter is Sanford was a major accent (Sanford Yellow Major Accent) ®, highlighter B, uh Barry Denny hand fluorescein cents a yellow hi-lighter was (Avery Dennison Fluorescent Yellow Hi-Liter ) ®.

Figure 112010017976960-pct00040

[Table 17 Continued]

Figure 112010017976960-pct00041

$ Ink Set 3 uses Epson photo paper instead of Office Depot 104.

Example 54

The following ink bases were prepared according to the procedure described below and used to prepare the final ink with color dispersion.

Figure 112010017976960-pct00042

First, 12.3% by weight of water was added to a clean vessel. The mixing device was then placed in the vessel to shake the water and to provide mixing while adding the other ingredients. Mixing was performed using a magnetic stirrer. Next, 14% by weight of glycerin, 2% by weight of PEG 600, 3% by weight of butyl carbitol, 2% by weight of ethanol and 1% by weight of butanol were added to the vessel. This was dissolved. Then, 0.1 wt% of triethanolamine was added and dissolved. Finally, 0.3 wt% of Cobratec solution and 0.3 wt% of Xbinx 19G were added and dissolved.

Example 55

The following inks were prepared according to the procedure described below.

Figure 112010017976960-pct00043

[Table 19 Continued]

Figure 112010017976960-pct00044

A second vessel was prepared by adding the calculated weight percent deionized water to the vessel according to Table 19 for the pigment dispersion. Subsequently, the magnetic stirring apparatus was placed in the vessel. Next, an ink base, followed by a surpinol surfactant (available from Air Products and Chemicals, Inc., Allentown, PA) was slowly added to the pigment dispersion in the second vessel. The dispersion was mixed during this process. After all the diluents have been added, the ink is mixed for about 1 hour or until completely homogeneous. After mixing, the ink was filtered using a 1 [mu] m glass filter (available from Watman, Kent, England).

The printing performance characteristics of the color ink were confirmed as follows.

Figure 112010017976960-pct00045

[Table 20 Continued]

Figure 112010017976960-pct00046

Figure 112010017976960-pct00047

[Table 21 Continued]

Figure 112010017976960-pct00048

Figure 112010017976960-pct00049

[Table 22 Continued]

Figure 112010017976960-pct00050

Example 56

Wood stain application performance

The woodstain was prepared from a 6% dry pigment loaded with 18% resin Joncryl 95 (available from Johnson Polymer, Stetevant, WI) and balanced solution of deionized water And tested. Drawdown on a Leneta Form 3NT-3 using a wire-wound rod # 7 (available from Paul N. Gardner Company, Pompano Beach, Fla.). ) Was performed with a 1 "x4" strip. Half of each strip was immersed in deionized water for 1 minute. The strips were dried at ambient temperature. The color difference (DE * ) was read by a spectrophotometer. A lower DE * indicates better waterfastness.

Figure 112010017976960-pct00051

Example 57

Coating performance

The following coating formulation (Masstone) was prepared and tested in a 6% dry pigment loaded with a 25% acrylic vehicle (available from Valspar, Wheeling, Illinois) and balanced solution of deionized water . A drawdown was made on Reneta Foam 2A using 6.0 mil wire-wound rods. Chemical resistance was measured individually by spotting 10 droplets of 10% hydrochloric acid and 10 droplets of 10% sodium hydroxide solution on the milestone drawdown. The degree of chemical resistance was measured by obtaining the DE * value between the spotted area and the control area.

Figure 112010017976960-pct00052

Figure 112010017976960-pct00053

Example 58

Color filter application performance

The following color filter formulation was adjusted to a total of 75% deionized water followed by a 30% valsarpal acrylic vehicle, 30% Zoncryl 1972 (available from Johnson Polymer, Stutton, WI) and 40% 1-methoxy- (25%) consisting of propanol (propylene glycol monomethyl ether) and 6% dry pigment loading. After drying at ambient temperature, the transmission value of the color filter coating on a transparent olefin polymer substrate using wire-wound rod # 7 (available from Paul N. Gardner Company, Pompano Beach, FL) was measured.

Figure 112010017976960-pct00054

Example 59

Fabric printing application performance

The following printing paste was prepared and tested with Delta Ceramcoat Textile Medium 16 (33%), Valspar acrylic vehicle (5%) and 6% dry pigment loaded with balanced deionized water. Using a 6.0-mill wire-wound rod, a drawdown of the printing paste on a white cotton fabric was prepared. After drying at ambient temperature, the prints were heat set at 140 占 폚 in the oven for 10 minutes. The fabric was cut into 1 "x4" strips and half (1 "x2") of each strip was immersed in boiling deionized water for 5 minutes. The exposed strips were then washed in cold tap water for one minute and dried at ambient temperature. Wash fastness and waterfastness were evaluated by measuring the total color change (DE * ) between the control and the treated fabric.

Figure 112010017976960-pct00055

16 was adjusted to 23% DCTM and 2% VAV for two PB 15 pigment dispersions.

Claims (53)

  1. Reacting the cyanuric chloride with three equivalents of a second compound comprising an amine or a mixture of a second compound comprising an amine to displace all reactive chlorine to form the substituted triazine; And
    Reacting the substituted triazine with the surface of the pigment using a radical initiator to form a surface modified pigment
    &Lt; / RTI &gt;
  2. The method of claim 1, wherein the radical initiator comprises persulfate.
  3. The method of claim 1, wherein the mixture of secondary compounds may comprise one, two, or three different secondary compounds.
  4. The process according to any one of claims 1 to 3, which is carried out at a temperature of from 25 캜 to 90 캜.
  5. 4. The method according to any one of claims 1 to 3, wherein the secondary compound is selected from the group consisting of amino benzoic acid, aminobenzenesulfonic acid, aminophenol, aminosulfonic acid, polyethoxylated amino acid, sodium sulfanilate, Aminophenolate, taurine, oleic acid (amino), sodium aminooleate, an organic polymeric substrate, a linear poly (aminobenzoate), an aminobenzoate, At least one of an ethoxy polymer amine, a linear propoxy polymer amine, a diamino aromatic, a polyethyleneimine, a polyguanidine, a quaternary ammonium compound, or a combination thereof.
  6. 4. The process according to any one of claims 1 to 3, wherein the pigment is selected from the group consisting of carbon black, red pigment 122, violet pigment 19, violet pigment 23, red pigment 202, red pigment 188, yellow pigment 155, yellow pigment 97, 7, blue pigment 15: 3, blue pigment 15: 4, and yellow pigment 74, and combinations thereof.
  7. 4. The method according to any one of claims 1 to 3, further comprising milling the pigment to less than 100 nm before, during, or after the reaction with the substituted triazine.
  8. 4. The process according to any one of claims 1 to 3, wherein the surface-modified pigment comprises from 0.01 to 1.0 mMole of S and from 0.01 to 2.0 mMole of active hydrogen per gram of pigment.
  9. Reacting a reactive compound having an X- [Y] n reactive group with a second compound NS-ZM to form a substituted reactive intermediate [Y] a -X- (NS-ZM) b ; And
    Reacting the pigment with the substituted reactive intermediate [Y] a -X- (NS-ZM) b to form a surface-modified pigment by attaching the substituted reactive intermediate to the surface of the pigment;
    Wherein X is a sulfonyl, phosphoryl, or 1,3,5-triazinyl group;
    Y is a halogen leaving group;
    N is a nucleophilic group;
    S is an organic group;
    ZM is an ionizing end group;
    n is an integer from 1 to 3;
    b is an integer from 1 to 3;
    a = nb;
    Where n is equal to or greater than b;
    and when b is 2 or 3, each NS-ZM may be the same or different.
  10. 10. The method of claim 9 wherein b is 2 or 3 and each N-S-ZM is different.
  11. 10. The method of claim 9, wherein the pigment is in the form of a powder or wet cake and is milled with a grinding aid before reacting with the substituted intermediate.
  12. 12. The method according to any one of claims 9 to 11, wherein Y comprises at least one of fluorine, chlorine, bromine, or iodine.
  13. 12. The method according to any one of claims 9 to 11, wherein N comprises at least one of an amine, an imine, a pyridine, or a thiol group.
  14. 12. The method according to any one of claims 9 to 11, wherein S comprises at least one of substituted or unsubstituted alkyl, aryl and polymer chains having a molecular weight in the range of from 300 to 8000.
  15. 12. A compound according to any one of claims 9 to 11, wherein Z comprises at least one of a carboxyl, sulfonyl, phenolic, or phosphoryl group and M comprises at least one of a proton or cation in the form of a salt How it is.
  16. 12. The method according to any one of claims 9 to 11, wherein the secondary compound N-S-ZM comprises at least one of a polymer, an amine, an amino acid, an alcohol, a thiol, and combinations thereof.
  17. 12. The method according to any one of claims 9 to 11, wherein the secondary compound NS-ZM is selected from the group consisting of amino benzoic acid, aminobenzenesulfonic acid, aminophenol, aminosulfonic acid, polyethoxylated amino acid, sodium sulfanilate, sulfanilic acid, sodium p-aminobenzoate, p-aminophenol, ethyl 4-aminobenzoate, taurine, oleic acid (amino), tetramethylammonium 4-aminobenzoate, sodium 4-aminophenolate, sodium aminooleate, &Lt; / RTI &gt; and combinations thereof.
  18. 18. The composition of claim 17, wherein the organic polymeric substrate is a linear alkyl and branched ethoxy and propoxy polymer having a molecular weight of 300 to 3000, a linear polyethoxy polymer amine, a linear propoxy polymer amine, a styrene acrylic copolymer, a polyethyleneimine, &Lt; / RTI &gt; and combinations thereof.
  19. 12. The method according to any one of claims 9 to 11, wherein Z comprises at least one of ammonium, trimethylammonium, or tributylammonium, and M comprises at least one of halide or negatively charged ions .
  20. 20. The method of claim 19, wherein the secondary compound N-S-ZM comprises at least one of a diaminoaromatic, polyethyleneimine, polyguanidine, quaternary ammonium compound, or a combination thereof.
  21. 12. A pigment according to any one of claims 9 to 11, wherein the pigment is selected from the group consisting of carbon black, red pigment 122, violet pigment 19, violet pigment 23, red pigment 202, red pigment 188, yellow pigment 155, yellow pigment 97, green pigment 7 , Blue pigment 15: 3, blue pigment 15: 4, and yellow pigment 74, and combinations thereof.
  22. 12. The method according to any one of claims 9 to 11, further comprising milling the pigment to less than 100 nm before, during, or after the reaction with the substituted reactive intermediate.
  23. 12. A process according to any one of claims 9 to 11, wherein the substituted reactive intermediate [Y] a- X- (NS-ZM) b is associated with a charge-balance counterion, earth metal, NR 1 R 2 R 3 H +, and combinations of a method comprising at least one of a combination of the further step of at least partially substituted with the NR 1 R 2 R 3 H + at R 1, R 2, and R 3 is independently H or a substituted or unsubstituted C 1 -C 5 alkyl group.
  24. 24. The method of claim 23, wherein the counterion is to K +, Li +, NH 4 +, monoethanol ammonium, tetraethyl ammonium, triethanol ammonium, tetramethylammonium, tetrabutylammonium, and at least one of a combination of one, at least in part substituted Way.
  25. 12. The method according to any one of claims 9 to 11, wherein the surface-modified pigment comprises between 0.01 and 1.0 mMole of S and 0.01 to 2.0 mMole of active hydrogen per gram of pigment.
  26. 12. A pigment according to any one of claims 1 to 3 and 9 to 11, characterized in that the surface-modified pigment comprises from 0.06 to 0.7 mMoles of S and from 0.07 to 1.6 mMoles of active hydrogen per gram of pigment Way.
  27. 12. A process according to any one of claims 1 to 3 and 9 to 11, wherein the surface-modified pigment comprises 0.168 to 0.430 mMoles of S per gram of pigment and 0.07 to 0.313 mMoles of active hydrogen- 15. &Lt; / RTI &gt;
  28. 12. A pigment according to any one of claims 1 to 3 and 9 to 11, characterized in that the surface-modified pigment comprises 0.062 to 0.187 mMoles of S and 0.077 to 0.394 mMole of active hydrogen per g of pigment, 122 &lt; / RTI &gt;
  29. 12. A pigment according to any one of claims 1 to 3 and 9 to 11, wherein the surface-modified pigment comprises 0.131 to 0.178 mMoles of S per gram of pigment and 0.192 to 0.290 mMole of active hydrogen, 74. &Lt; / RTI &gt;
  30. 12. A pigment according to any one of claims 1 to 3 and 9 to 11, characterized in that the surface-modified pigment comprises from 0.103 to 0.702 mMoles of S per g of pigment and from 0.203 to 1.579 mMoles of active hydrogen &Lt; / RTI &gt;
  31. The method of any one of claims 1 to 3 and 9 to 11 wherein the surface modified pigment comprises sodium in an amount of 100 to 6500 ppm and potassium in an amount of 30 to 1200 ppm .
  32. 12. A process according to any one of claims 1 to 3 and 9 to 11, wherein the surface modified pigment comprises sulfur in an amount between 50 ppm and 2600 ppm.
  33. 12. A process according to any one of claims 1 to 3 and 9 to 11, wherein the surface modified pigment comprises
    0.7 to 2.7 atomic percent nitrogen, wherein 46 to 54 percent of the nitrogen is present in the NH group and the remainder is in the NC = N group;
    Oxygen having an atomic ratio of 6.8 to 20.9%, wherein at least 51 to 62% of the oxygen is present as a C = O, COONa, or SOx group and the remainder as a CO group, wherein SOx is the oxidized form of S;
    0.7 to 2.6 atom% COONa / SO 3 Na of
    Wherein the carbon black is a surface-modified carbon black comprising carbon black adhered to the surface of the carbon black,
    Wherein at least 90% of the S present on the surface-modified carbon black is oxidized S (SOx).
  34. 34. The process of claim 33, wherein the SOx comprises at least one of sulfone, sulfate, or sulfonic acid.
  35. 12. The method according to any one of claims 1 to 3 and 9 to 11, wherein the surface-modified pigment is a surface-modified blue pigment 15 comprising a surface oxygen content of at least 2.5 atomic%.
  36. 12. A pigment according to any one of claims 1 to 3 and 9 to 11, characterized in that the surface modified pigment comprises a surface oxygen content of 8.3 to 9.8 atomic%, wherein 24 to 32% Lt; RTI ID = 0.0 &gt; red-pigment &lt; / RTI &gt;
  37. 12. The pigment according to any one of claims 1 to 3 and 9 to 11, wherein the surface modified pigment comprises a surface oxygen content of 21.6 to 29.3 atomic%, wherein 42% to 48% , Surface modified yellow pigment 74 present as COONa / CSO 3 Na.
  38. 12. A process according to any one of claims 1 to 3 and 9 to 11, further comprising incorporating the surface modified pigment into an aqueous pigment dispersion.
  39. 12. A method according to any one of claims 1 to 3 and 9 to 11, wherein the surface modified pigment is incorporated into at least one of wood stain, coating, ink jet ink, color filter or printing ink, &Lt; / RTI &gt;
  40. 12. The compound according to any one of claims 9 to 11, wherein the X- [Y] n reactive group is cyanuric chloride and the second compound NS-ZM is 4-aminobenzoic acid, sulfanilic acid, 4-aminophenol, taurine, oleic acid Amino), linear polyethoxy polymer amine, propoxy polymer amine, or combinations thereof.
  41. 41. The method of claim 40, wherein the X- [Y] n reactive group is cyanuric chloride and the secondary compound is 4-aminobenzoic acid and a polymeric amine.
  42. 12. A process according to any one of claims 1 to 3 and 9 to 11 wherein the surface modified pigment is a self-dispersible pigment.
  43. Attaching a reactive group to the surface of the pigment; And
    And then replacing the reactive group with an organic substrate having an ionizing end group,
    Wherein the pigment is selected from the group consisting of red pigment 122, violet pigment 19, violet pigment 23, red pigment 202, red pigment 188, yellow pigment 155, yellow pigment 97, green pigment 7, blue pigment 15: 3, blue pigment 15: &Lt; RTI ID = 0.0 &gt; 74. &Lt; / RTI &gt;
  44. Attaching the reactive group XY to the surface of the pigment; And
    And then replacing Y with an organic substrate NS-ZM to form a surface-modified pigment with XNS-ZM attached thereto,
    Wherein X is a sulfonyl, phosphoryl, or 1,3,5-triazine group;
    Y is fluorine, chlorine, bromine, or iodine;
    N is an amine, an imine, a pyridine, or a thiol group;
    S is a substituted or unsubstituted alkyl, aryl, or polymer chain having a molecular weight in the range of from 300 to 8000;
    Z is a carboxyl, sulfonyl, phenolic, phosphoryl, ammonium, trimethylammonium, or tributylammonium group;
    And M is a halide, a negatively charged ion, a salt form proton, or a salt form cation.
  45. 45. The method of claim 44, wherein X is a sulfonyl group.
  46. 45. The method of claim 44, wherein the reactive group X-Y is attached to the surface of the pigment by chlorosulfonation with a chlorosulfonating agent comprising chlorosulfonic acid, thionyl chloride, or a combination thereof.
  47. 47. The method of claim 46, wherein the ratio of pigment to chlorosulfonating agent is at least 4: 1 (wt / wt).
  48. 47. The method of claim 46, wherein the ratio of pigment to chlorosulfonating agent is from 1:20 to 1: 1 (wt / wt).
  49. 47. The method of claim 46, wherein the chlorosulfonating agent is a mixture of chlorosulfonic acid and thionyl chloride in a ratio of 3: 1 to 6: 1 (wt / wt).
  50. 47. The process of claim 46, wherein the chlorosulfation is performed at a temperature of from 25 占 폚 to 160 占 폚.
  51. 50. The method according to any one of claims 44 to 50,
    Modifying most of the pigment surface to form a liquid gel; And
    Milling the liquid gel with an excess of untreated pigment and water to form a stable aqueous pigment dispersion
    &Lt; / RTI &gt;
  52. 52. The method of claim 51, wherein modifying the majority of the pigment surface comprises chlorosulfonating the pigment for at least 1 hour at a temperature of at least 90 DEG C to form the pigment sulfonyl chloride.
  53. delete
KR1020107006246A 2007-08-23 2008-08-22 Self-dispersed pigments and methods for making and using the same KR101575913B1 (en)

Priority Applications (2)

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